Cristina Pablos

Analogies and differences between photocatalytic oxidation of chemicals and photocatalytic inactivation of microorganisms

This study reports the analogies and differences found when comparing TiO(2) photocatalytic treatment for chemical oxidation and microorganisms inactivation, using methylene blue and Escherichia coli as references, respectively. In both processes the activation is based on the same physicochemical phenomena and consequently a good correlation between them is observed when analyzing the effect of operational variables such as catalyst concentration or incident radiation flux, both factors influencing common stages such radiation absorption and generation of reactive oxygen species. However, different microbiological aspects (osmotic stress, repairing mechanism, regrowth, bacterial adhesion to the titania surface, etc) makes disinfection kinetics significantly more complex than the first-order profiles usually observed for the oxidation of chemical pollutants. Moreover, bacterial inactivation reactions are found to be extremely sensitive to the composition of water and modifications of the catalysts in comparison with the decolorization of the dye solutions, showing opposite behaviors to the presence of chlorides, incorporation of silver to the catalysts or the use of different types of immobilized TiO(2) systems. Therefore, the activity observed for the photocatalytic oxidation of organics can not be always extrapolated to photocatalytic disinfection processes.

Emerging micropollutant oxidation during disinfection processes using UV-C, UV-C/H2O2, UV-A/TiO2 and UV-A/TiO2/H2O2.

Regeneration of wastewater treatment plant effluents constitutes a solution to increase the availability of water resources in arid regions. Water reuse legislation imposes an exhaustive control of the microbiological quality of water in the operation of disinfection tertiary treatments. Additionally, recent reports have paid increasing attention to emerging micropollutants with potential biological effects even at trace level concentration. This work focuses on the evaluation of several photochemical technologies as disinfection processes with the aim of simultaneously achieving bacterial inactivation and oxidation of pharmaceuticals as examples of emerging micropollutants typically present in water and widely studied in the literature. UV-C-based processes show a high efficiency to inactivate bacteria. However, the bacterial damages are reversible and only when using H(2)O(2), bacterial reproduction is affected. Moreover, a complete elimination of pharmaceutical compounds was not achieved at the end of the inactivation process. In contrast, UV-A/TiO(2) required a longer irradiation time to inactivate bacteria but pharmaceuticals were completely removed along the process. In addition, its oxidation mechanism, based on hydroxyl radicals (OH), leads to irreversible bacterial damages, not requiring of chemicals to avoid bacterial regrowth. For UV-A/TiO(2)/H(2)O(2) process, the addition of H(2)O(2) improved Escherichia coli inactivation since the cell wall weakening, due to OH attacks, allowed H(2)O(2) to diffuse into the bacteria. However, a total elimination of the pharmaceuticals was not achieved during the inactivation process.

Comparative evaluation of acute toxicity by Vibrio fischeri and fern spore based bioassays in the follow- up of toxic chemicals degradation by photocatalysis

The development of efficient bioassays is a necessary step for cost-effective environmental monitoring and evaluation of novel decontamination technologies. Marine Vibrio fischeri kits have demonstrated to be extremely sensitive but lack of ecological relevance, especially when assessing impacts on freshwater higher organisms. A novel riparian are fern spore microbioassay could merge higher ecological relevance and reduced costs. The aim of this work is the comparative evaluation of the V. fischeri and fern spore bioassays for the follow up of detoxification processes of water contaminated with cyanide and phenol by advanced oxidation technologies, using heterogeneous photocatalysis as example. In both cases, EC(50) values differed significantly for V. fischeri commercial kit, V. fischeri lab cultures and Polystichum setiferum fern spores (1.9, 16 and 101 mg cyanide L(-1) and 27.0, 49.3 and 1440 mg phenol L(-1), respectively). Whereas V. fischeri bioassays are extremely sensitive and dilution series must be prepared, toxicant solutions can be directly applied to spores. Spore microbioassay was also useful in the follow up of photoxidation processes of cyanide and phenol, also reflecting the formation of intermediate degradation by-products even more toxic than phenol. We conclude that this new microbioassay is a promising cost-effective tool for the follow up of decontamination processes.

Simultaneous photocatalytic oxidation of pharmaceuticals and inactivation of Escherichia coli in wastewater treatment plant effluents with suspended and immobilised TiO(2).

Simultaneous Escherichia coli inactivation and oxidation of pharmaceuticals in simulated wastewater treatment plant effluents has been investigated using a photocatalytic treatment with TiO(2) in suspension and immobilised onto a fixed-bed reactor. Non-photocatalytic reference experiments of dark adsorption and photolysis showed a higher sensitivity of E. coli towards the chemical composition of water in comparison with the concentration of pharmaceuticals that remains unaffected. Moreover, it must be underlined that the presence of pharmaceuticals (including antibiotics) did not seem to affect the bacterial viability at such low concentrations. Concerning photocatalytic experiments, both suspended and immobilised TiO(2) were able to simultaneously inactivate and oxidise both kinds of pollutants (bacteria and pharmaceuticals). The fixed-bed reactor showed similar activity to that of the slurry without deactivation after several cycles of reuse. That makes TiO(2) photocatalysis a quite interesting technology for the treatment of drinking water supplies or wastewater plant effluents, allowing the removal of emerging contaminants such as pharmaceuticals during the disinfection treatment.

Kinetics and influence of water composition on photocatalytic disinfection and photocatalytic oxidation of pollutants.

This work is focused on the comparison between the photocatalytic inactivation of Escherichia coli and the photocatalytic oxidation of methylene blue, regarding the reaction kinetics and the influence of water composition. Disinfection profiles show an initial delay, in contrast with the exponential decay shown by the decolorization of methylene blue solutions. A serial‐event mechanism is proposed for both disinfection and mineralization processes, the number of intermediate species being the main difference between them. Concerning the influence of water composition, inactivation of bacteria is more sensitive to the presence of inorganic ions and/or organic matter in the solution. In some cases opposite behaviours are observed, such as in the presence of chloride ions, which enhance the disinfection rate but decrease degradation activity for methylene blue. Consequently, the results obtained in the evaluation of photocatalytic processes for the degradation of chemical pollutants cannot be always extrapolated to the inactivation of microorganisms.

Electrochemical Enhancement of Photocatalytic Disinfection on Aligned TiO2 and Nitrogen Doped TiO2 Nanotubes

TiO2 photocatalysis is considered as an alternative to conventional disinfection processes for the inactivation of waterborne microorganisms. The efficiency of photocatalysis is limited by charge carrier recombination rates. When the photocatalyst is immobilized on an electrically conducting support, one may assist charge separation by the application of an external electrical bias. The aim of this work was to study electrochemically assisted photocatalysis with nitrogen doped titania photoanodes under visible and UV-visible irradiation for the inactivation of Escherichia coli. Aligned TiO2 nanotubes were synthesized (TiO2-NT) by anodizing Ti foil. Nanoparticulate titania films were made on Ti foil by electrophoretic coating (P25 TiO2). N-doped titania nanotubes and N,F co-doped titania films were also prepared with the aim of extending the active spectrum into the visible. Electrochemically assisted photocatalysis gave higher disinfection efficiency in comparison to photocatalysis (electrode at open circuit) for all materials tested. It is proposed that electrostatic attraction of negatively charged bacteria to the positively biased photoanodes leads to the enhancement observed. The N-doped TiO2 nanotube electrode gave the most efficient electrochemically assisted photocatalytic inactivation of bacteria under UV-Vis irradiation but no inactivation of bacteria was observed under visible only irradiation. The visible light photocurrent was only a fraction (2%) of the UV response.

Photoelectrocatalytic study and scaling up of titanium dioxide electrodes for wastewater treatment

Different TiO2 photoelectrodes have been characterized and tested for the photoelectrocatalytic oxidation of methanol. Particulate electrodes (TiO2/Ti and TiO2/ITO) have been shown to notably favour charge-carrier transfer at the electrolyte interface while a thermal electrode (Ti) has been shown to favour charge-carrier separation when applying an electric potential bias according to cyclic voltammetry technique, as a consequence of differences in TiO2 surface between particulate and thermal electrodes. Particulate electrodes lead to a higher photoelectrocatalytic activity for methanol oxidation compared to that of the thermal electrode, probably due to the pure-rutile TiO2 phase composition of the latter and its lower surface area. TiO2/Ti electrode has been shown to be the most effective photoelectrode tested for methanol oxidation since its activity was improved by the combination of the particulate TiO2 layer and the high electrical conductivity of the support. Generally, photocurrent density measured in the photoelectrochemical cell seems to correlate with activity, whereas this correlation is not observed when using a larger photoelectrocatalytic reactor. In contrast, the activity obtained for the scaled-up electrode is found to be similar in terms of surface kinetic constant to that obtained at laboratory scale.

Determination of Photochemical, Electrochemical and Photoelectrochemical Efficiencies in a Photoelectrocatalytic Reactor

Abstract The relation between the amount of incident photons, absorbed photons, oxidant species, reaction products and electrons in the external circuit should be analyzed individually to determine the step limiting the efficiency of the global photoelectrocatalytic processes. This work discusses the evaluation of three different titania electrodes for the oxidation of methanol in a photoelectrocatalytic reactor. The electrode prepared with three titania coating cycles shows a high efficiency in terms of photochemical (photons to product molecules), electrochemical (product molecules to electrons) and photoelectrochemical (photons to electrons) what explain its high activity for the photoelectrocatalytic oxidation of methanol.

Implications of Electrical Impedance-Based Microbiological Technology in Pork Meat Processing Industry for the Rapid Detection and Quantification of Salmonella Spp.

The absence of efficient tools for preventing bacterial contamination in the meat processing industry as well as for detecting Salmonella positive samples in real time is a matter of concern. Impedance technology has proved its effectiveness as a bacterial quantification tool for research purposes instead of laborious standard plate count, and as a detection tool to substitute tedious current horizontal method ISO 6579:2002. Calibration curves were carried out for S. enteritidis and S. typhimurium in raw pork matrix (R > 0.90). Calibrations of mixtures of both strains at different ratio were prepared, showing a high efficiency to differentiate bacterial metabolism. Impediometry was also validated against standard plate count in raw pork samples treated by UV-C illumination to inactivate Salmonella. Even, damaged but still viable bacteria were recorded. Detection of Salmonella by impediometry led to a decrease in false positives, obtaining results within 30 h compared to 72 h in case of conventional method.

Effects of natural antimicrobials on prevention and reduction of bacterial cross-contamination during the washing of ready-to-eat fresh-cut lettuce:

Microbiological safety of the fresh-cut produce may not be guaranteed if the quality of wash water is not maintained. The use of natural antimicrobials as alternative to chlorine may offer interesting possibilities for disinfecting wash water. Antimicrobial properties of allyl- and benzyl-isothiocyanates, respectively, and chitosan against Salmonella spp. were evaluated by standard plate count. Minimal inhibitory concentration values were observed for benzyl-isothiocyanate and chitosan, corresponding to 50 and 1000 mgl−1, respectively. A 5 min washing of 25 g fresh-cut lettuce was performed. Transfer of Salmonella from the water to the produce was observed. Benzyl-isothiocyanate addition of 75 mgl−1 before starting the washing process gave rise to a complete removal of total bacteria and Salmonella in the wash water after 24 h before starting the second cycle. Antimicrobial benzyl-isothiocyanate effects have been demonstrated to persist after 48 h.