Photocatalytic degradation of humic acid using a novel photocatalyst: Ce-doped ZnO.

This study aimed at investigating the photocatalytic degradation of humic acid (HA) as a representative of natural organic matter (NOM) by using Ce-doped ZnO as a novel material. Following photocatalysis, HA degradation was characterized by specified UV-vis and fluorescence spectroscopic parameters as well as by the dissolved organic carbon (NPOC) content. Excitation-Emission Matrix (EEM) fluorescence features were also evaluated by using advanced techniques. Comparison of Ce-doped ZnO photocatalysis to TiO2 P-25 photocatalytic treatment of the HA samples was elucidated under similar experimental conditions. Kinetic modeling of the photocatalytic removal of HA expressed promising results indicating that Ce-doped ZnO could serve as an efficient catalyst for the degradation of NOM.

The effect of photocatalytic oxidation on molecular size distribution profiles of humic acid.

The influence of photocatalytic degradation on molecular size fractionation (0.45 µm filtered, 100 kDa, 30 kDa and 3 kDa) of humic acid as a model compound of natural organic matter was investigated. The results were evaluated using UV-vis parameters, dissolved organic carbon (DOC) and excitation emission matrix (EEM) fluorescence spectral features. EEM fluorescence signatures displayed an irradiation period dependent transformation of humic-like fluorophores to fulvic-like fluorophores in accordance with the photocatalytic mineralization of HA. Molecular size distribution profiles expressed the formation of lower molecular size (<3 kDa) fractions through oxidative degradation of humic acid of higher molecular size fractions (100 kDa and 30 kDa fractions). The fluorescence-derived index (fluorescence intensity (FI), represented by the ratio of the emission intensity at λemis = 450 nm to that at λemis = 500 nm, following the excitation at λexc = 370 nm) was also investigated. The use of EEM features has proven to be a useful tool for monitoring the effect of photocatalytic degradation on the structure and molecular size distribution profile of HA.

Significance of analytical parameters for the understanding of natural organic matter in relation to photocatalytic oxidation.

In this review, special interest was devoted to provide information on the surrogate parameters expressing both quality and quantity of organic matter for the understanding of the photocatalytic oxidation of humic substances. Detailed investigation was directed to the application of photocatalysis with reference to source, origin and modeling of organic matter. Evaluation of the literature findings emphasizes that organic matter taken from natural waters are site specific and should be characterized in detail to be comparable to other studies. Taking into account the photocatalytic degradation studies of natural organic matter, humic substances, humic acids and fulvic acids in slurry systems, a procedure could be deduced that depends on the selection of a standard model sample with a representative concentration, selection of a standard photocatalyst and dose (e.g., TiO2 Degussa P-25, 0.25 mg mL(-1)), application of standardized reaction conditions such as light intensity, pH, and temperature. Furthermore, standardized filtration step avoiding organic leaching and selection of the most suitable analytical parameter are the crucial points to be considered. The use of such a protocol could form a basis for the determination of "relative degradation efficiency" of any sample containing natural organic matter, humic substances, humic acids and fulvic acids regardless of dependency on source and origin.

TiO(2)-assisted photocatalytic degradation of humic acids: effect of copper ions.

The present study investigated the removal efficiency of aqueous humic acid solutions by TiO(2) photocatalytic degradation in the presence of Cu(II) species. The pseudo-first-order kinetics revealed rate constants as 9.87 x 10(-3), 7.19 x 10(-3), 3.81 x 10(-3) min(-1) for Color(436), UV(254) and TOC, respectively. Comparatively, lower rate constants were attained with respect to photocatalytic degradation of humic acid. Considering the source-dependent diverse chemical and spectral characteristics of NOM, a particular interaction would be expected for humic acid with Cu(II) species (0.1 mg L(-1)). The presence of copper ions significantly altered the photocatalytic degradation kinetics of humic acids in relation to the concentration effects of humic acid as expressed by spectroscopic parameters and TOC. Batch equilibrium adsorption experiments revealed a distinct Langmuirian-type adsorptive behavior of humic acid onto TiO(2) both in terms of UV(254) and Color(436) and a C-type adsorption isotherm was attained for TOC. K(F) values displayed an inconsistent effect of Cu(II) species, while adsorption intensity factor 1/n<1 denoted a prevailing favorable type of adsorption for Color(436) and UV(254). Because of the role of intra- and intermolecular interactions between copper ions and humic molecular size fractions, spectroscopic techniques were also employed for the assessment of the adsorption as well as photocatalytic degradation efficiencies.

Activation of solgel titanium nanofilm by UV illumination for NOM removal.

The control of natural organic matter (NOM) in drinking water treatment plants is required in order to control (i) the formation of potentially harmful disinfection byproducts (DBPs), (ii) the regrowth of bacteria and (iii) pipe corrosion in the distribution system. Photocatalysis is a promising advanced oxidation technology due to its ability to mineralise chlorinated byproduct precursors such as humic acids (HAs) to carbon dioxide and water. In this study, the efficiency of HAs and NOM removal in terms of UV absorbance at 254 nm (UV254) was tested by means of a new photocatalytic reactor made of stacked polymethylmethacrylate (PMMA) rings coated by TiO2 nanofilm. Three different sets of rings were coated with TiO2 gel one, two and three times respectively to optimise the coating thickness according to UV254 removal efficiency. The titania sol was immobilised on the substrate by a low temperature procedure and after 8 months the reactors were reactivated by means of UV radiation before the experiments. The photocatalytic removal efficiency of humic acid in terms of UV254 was significantly higher after 1 hour for the reactor employed with high thickness TiO2 nanofilm (around 20%) compared to middle and low thickness reactors (6 and 1.4%, respectively). However, during the same reaction time only 10% of UV254 was removed with high thickness TiO2 nanofilm using raw surface water, probably owing to ionic species naturally occurring in the raw water sample. Finally, the activation of the TiO2 nanofilm may be effectively accomplished by means of UV radiation where calcination cannot be applied (e.g. thermally sensitive substrates).

Effects of oxidative treatment techniques on molecular size distribution of humic acids.

In this study ultrafiltration has been used for the fractionation of humic acid samples. Humic acids were treated in a sequential oxidation system in which ozonation was followed by photocatalytic oxidation using TiO2. Evaluation of the spectroscopic characteristics of the oxidized and fractionated humic acid samples have shown that molecular size distribution ranges shift to lower molecular sizes depending on the oxidation stages. Applied ozone dosage and irradiation time during the photocatalysis stage are the factors affecting the molecular size distribution in the treated humic acid samples. Formation of lower molecular weight compounds during the ozonation stage resulted in increased degradation rates during the photocatalysis stage.

An innovative photocatalytic technology in the treatment of river water containing humic substances.

This study addresses the application of a photoelectrocatalytic (PEC) system with separated hole and electron reactions to treat humic acid (HA) from river water. A TiO2 electrode, coated by the sol-gel method, is used for that purpose. The degradation of humic acid in the river water was followed with respect to time using parameters of UV254, color and total organic carbon (TOC). For comparison purposes the photocatalytic (PC) removal of HA was also studied on the same photoanode. The obtained results showed that the PEC system was much more effective than the PC method. The effect of other important reaction variables, such as external potential, oxygen and UV intensity on HA degradation were also investigated. For all the external applied potential conditions and UV intensity range over 90% removal of UV254 and color were obtained with the PEC system while TOC removal was between 58-80%.

Interactions of hypochlorite ion and humic acid: photolytic and photocatalytic pathways.

Photolytic and photocatalytic interactions of hypochlorite ion and humic acid are investigated under various conditions. Humic acid oxidation by aqueous chlorine under dark conditions are expressed in terms of first order reaction kinetics. Upon irradiation (300 nm < lambda < 400 nm), photolysis of aqueous chlorine affect the removal efficiency of humic acid via oxidation. TiO2 sensitised photocatalytic oxidation conditions reveal an increase in the TOC removal rate of humic acid in the presence of aqueous chlorine. Under the specified conditions, increasing the photocatalyst loading up to 1.0 mg/mL markedly increase the TOC removal rate.

Inactivation of Escherichia coli by photocatalytic oxidation.

The inactivation of Escherichia coli (E.coli) was studied in presterilized surface water sample using titanium dioxide as the photocatalyst under irradiation of BLF Fluorescent lamps. Inactivation of E.coli (10(3) CFU/mL) was achieved in 60 min in the presence of 1.0 mg TiO2/mL. Photocatalytic inactivation data was evaluated in terms of first order rate equation N/N0 = e (-kIt). The reaction rate constant k, 1.22*10(-2)(mW min/cm2)-1 was calculated.