Comparison of radiant intensity in aqueous media using experimental and numerical simulation techniques.

Accurately modelling the propagation of radiant intensity in aqueous environments poses significant challenges for both academia and industry, due to complex interactions like absorption, scattering, and reflection. This study aims to improve the accuracy of optical modeling in water-based systems by comparing experimental data with numerical simulation techniques, addressing the need for more reliable simulation methods in multiple applications like treatment of water and environmental monitoring.Implementation has been done by analyzing how the method compares with the discrete ordinate method, radiometry, and actinometry. The study further quantifies the effect of the photoreactor quartz tube on measured intensity for multiple wavelengths. Losses in light intensity are estimated to be 10 ± 0.5% for FX-1 265 source. In contrast, the simulation in a water medium showed an increase of up to 64% in the light intensity delivered to the central part of the tube due to internal reflections and scattering. Model predictions from ray tracing successfully compared with the Discrete Ordinate Method (DOM) and experimental data (within ± 6%), ensuring the accurate design of complex systems for water disinfection. The data from simulations is seen to tackle challenges faced in complex radiation modeling and demonstrates that the method can be utilized as a useful tool for optimization and prediction.

Wavelength synergistic effects in continuous flow-through water disinfection systems.

The past decade's development of UV LEDs has fueled significant research in water disinfection, with widespread debate surrounding the potential synergies of multiple UV wavelengths. This study analyses the use of three UV sources (265, 275, and 310 nm) on the inactivation of Escherichia coli bacteria in two water matrixes. At maximum intensity in wastewater, individual inactivation experiments in a single pass set-up (Flow rate = 2 L min-1, Residence time = 0.75 s) confirmed the 265 nm light source to be the most effective (2.2 ± 0.2 log units), while the 310 nm led to the lowest inactivation rate (0.0003 ± 7.03×10-5 log units). When a combination of the three wavelengths was used, an average log reduction of 4.4 ± 0.2 was observed in wastewater. For combinations of 265 and 275 nm, the average log reductions were similar to the sum of individual log reductions. For combinations involving the use of 310 nm, a potential synergistic effect was investigated by the use of robust statistical analysis techniques. It is concluded that combinations of 310 nm with 265 nm or 275 nm devices, in sequential and simultaneous mode, present a significant synergy at both intensities due to the emission spectra of the selected LEDs, ensuring the possibility of two inactivation mechanisms. Finally, the electrical energy per order of inactivation found the three-wavelength combination to be the most energy efficient (0.39 ± 0.05, 0.36 ± 0.01 kWh m-3, at 50% and 100% dose, respectively, in wastewater) among the synergistic combinations.

Role of the active chlorine generated in situ on the photoelectrocatalytic inactivation of bacteria and fungi with TiO2 nanotubes.

Immobilised TiO2 nanotube (TiO2-NT) electrodes were grown via electrochemical anodisation in an aqueous solution containing fluoride ions at 10, 20 and 30 V. The photocatalytic (PC) and photoelectrocatalytic (PEC) activity of TiO2-NTs electrodes in the oxidation of methanol and the inactivation of bacteria and fungi was studied in different chloride salts electrolytes. Low concentrations of electrochemically generated oxidising species, such as free chlorine, were measured in experiments at pH 8.5 and +1 V of applied potential. Increasing the anodising potential results in longer nanotubes with higher photoactivity. The TiO2-NT electrode anodised at 30 V (TiO2-NT30V) generates free chlorine with an average concentration of 0.03 mg·L-1 upon illumination with UV-A at +1 V of potential bias. This concentration was enough to achieve 99.99 % of inactivation of a 106 CFU·mL-1 Gram-negative bacteria (Escherichia coli) in <3 min and Gram-positive bacteria (Enterococcus faecalis) after 7 min, whereas fungi (Candida albicans) required 15 min. The low production of chlorine was found to have a big impact on the bacteria and fungi inactivation even in not favourable chlorine generation conditions. An in situ investigation of the most influential parameters in the inactivation of some microorganisms with PEC and NT30V electrode has been done. It was found that free chlorine production increases with the length of TiO2-NT, with Cl- concentration up to 15 mmol·L-1 and with the application of potential bias. TiO2-NT30V photoanode has been demonstrated to produce active chlorine at levels compatible with the water disinfection process, suggesting that the present method could be considered a promising alternative for in situ chlorine-based disinfection.

Evaluation of the uniformity of UVA LED illumination on flat surfaces: Discrete ordinate method, single axis, and surface scanning radiometry.

Uniform illumination from UVA LED lamps is a crucial design characteristic for a range of industries including photocatalytic applications. In this work, radiometry and the discrete ordinate method (DOM) are used to determine the ideal target surface size and working distance from a UVA LED lamp for highly uniform illumination. Horizontal incident radiation and full surface incident radiation measurements were conducted using a scanning radiometry technique. It is shown that horizontal incident and full surface incident radiation measurements show good agreement for uniformity measurements over a range of working distances, with maximum uniformity (2.6% and 3.6% standard deviation respectively) over the measured range found at 15 mm working distance. DOM simulation results showed good agreement with radiometry for power and incident radiation measurements, whilst indicating a maximum uniformity at 20 mm working distance. These results demonstrate that DOM simulations can be used as a fast, low cost, and reliable indication of surface uniformity, peak surface irradiance, and power measurements in the design of UV lamps for industrial and academic applications.

A review on LED technology in water photodisinfection.

The increase in efficiency achieved by UV LED devices has led to a compelling increase in research reports on UV LED water treatment for consumption in the past few years. This paper presents an in-depth review based on recent studies on the suitability and performance of UV LED-driven processes for water disinfection. The effect of different UV wavelengths and their combinations was analysed for the inactivation of various microorganisms and the inhibition of repair mechanisms. Whereas 265 nm UVC LED present a higher DNA damaging potential, 280 nm radiation is reported to repress photoreactivation and dark repair. No synergistic effects have been proved to exist when coupling UVB + UVC whereas sequential UVA-UVC radiation seemed to enhance inactivation. Benefits of pulsed over continuous radiation in terms of germicidal effects and energy consumption were also analysed, but with inconclusive results. However, pulsed radiation may be promising for improving thermal management. As a challenge, the use of UV LED sources introduces significant inhomogeneities in the light distribution, pushing for the development of adequate simulation methods to ensure that the minimum target dose required for the target microbes is achieved. Concerning energy consumption, selecting the optimal wavelength of the UV LED needs a compromise between the quantum efficiency of the process and the electricity-to-photon conversion. The expected development of the UV LED industry in the next few years points to UVC LED as a promising technology for water disinfection at a large scale that could be competitive in the market in the near future.

Growth and prevalence of antibiotic-resistant bacteria in microplastic biofilm from wastewater treatment plant effluents.

It is accepted that Microplastic (MP) biofilms accumulates antibiotic-resistant bacteria (ARB) and antibiotic-resistant genes (ARGs) in water. ARB/ARGs and MPs are emerging pollutants of concern due to various associated health risks. The objective of this study was to 1) investigate the ARB community in a pilot-scale wastewater treatment plant (WWTP) effluent, 2) to study and visualize the ARB/ARGs in MP biofilm grown in WWTP effluent and tap water, and 3) to analyze microplastic adherent ARB/ARGs in the biofilm and planktonic ARB/ARGs in the filtrate under controlled conditions. Results indicated the dominance of Pseudomonas, Aeromonas, and Bacillus among isolated ARB in WWTP effluent. Representative resistance strains were incubated in 300 mL water containing commercial polystyrene beads of 300550 µm diameter (MP) in a series of batch experiments. Microbiological, molecular, and microscopic analyses were performed by enumeration, 16srRNA, real-time polymerase chain reaction (qPCR), and Field Emission-Scanning Electron Microscopy (FEG-SEM) techniques. The analyzed viable ARB indicated an increasing trend in MP biofilms between days 3 and 5. It further decreased on days 7 and 9. The prevalence of ARB in the filtrate and MP biofilm varied as a function of time and TOC level, while no significant impacts were observed for minor temperature variation, low antibiotic pressure, and increased MP mass with few exceptions. Relative abundance of ARGs (vanA, sul1) and integron integrase gene (intl1) in MP biofilm were significantly different across different TOC levels, time, and antibiotic pressure. ARGs and intl1 were detected in the MP biofilm in tap water and WWTP effluent on day 30.

Material selection and prediction of solar irradiance in plastic devices for application of solar water disinfection (SODIS) to inactivate viruses, bacteria and protozoa.

Solar water disinfection (SODIS) is a simple, inexpensive and sustainable Household Water Treatment (HWT) that is appropriate for low-income countries or emergency situations. Usually, SODIS involves solar exposure of water contained in transparent polyethylene terephthalate (PET) bottles for a minimum of 6 h. Sunlight, especially UVB radiation, has been demonstrated to photoinactivate bacteria, viruses and protozoa. In this work, an in-depth study of the optical and mechanical properties, weathering and production prices of polymeric materials has been carried out to identify potential candidate materials for manufacturing SODIS devices. Three materials were ruled out (polystyrene (PS), polyvinyl chloride (PVC) and polyethylene (PE)) and four materials were initially selected for study: polymethylmethacrylate (PMMA), polypropylene (PP), polycarbonate (PC) and polyethylene terephthalate (PET). These plastics transmit sufficient solar radiation to kill waterborne pathogens with production costs compensated by their durability under solar exposure. A predictive model has been developed to quantitatively estimate the radiation available for SODIS inside the device as a function of the material and thickness. This tool has two applications: to evaluate design parameters such as thickness, and to estimate experimental requirements such as solar exposure time. In this work, this model evaluated scenarios involving different plastic materials, device thicknesses, and pathogens (Escherichia coli bacterium, MS2 virus and Cryptosporidium parvum protozoon). The developed Solar UV Calculator model is freely available and can be also applied to other customized materials and conditions.

Assessment of full-scale tertiary wastewater treatment by UV-C based-AOPs: Removal or persistence of antibiotics and antibiotic resistance genes?

This research reports for the first time the full-scale application of different homogeneous Advanced Oxidation Processes (AOPs) (H2O2/UV-C, PMS/UV-C and PMS/Fe(II)/UV-C) for the removal of antibiotics (ABs) and antibiotic resistance genes (ARGs) from wastewater effluent at Estiviel wastewater treatment plant (WWTP) (Toledo, Spain). AOPs based on the photolytic decomposition of H2O2 and peroxymonosulfate tested at low dosages (0.05-0.5 mM) and with very low UV-C contact time (4-18 s) demonstrated to be more efficient than UV-C radiation alone on the removal of the analyzed ABs. PMS (0.5 mM) combined with UV-C (7 s contact time) was the most efficient treatment in terms of AB removal: 7 out of 10 ABs detected in the wastewater were removed more efficiently than using the other oxidants. In terms of ARGs removal efficiency, UV-C alone seemed the most efficient treatment, although H2O2/UV-C, PMS/UV-C and PMS/Fe(II)/UV-C were supposed to generate higher concentrations of free radicals. The results show that treatments with the highest removal of ABs and ARGs did not coincide, which could be attributed to the competition between DNA and oxidants in the absorption of UV photons, reducing the direct photolysis of the DNA. Whereas the photolytic ABs removal is improved by the generation of hydroxyl and sulfate radicals, the opposite behavior occurs in the case of ARGs. These results suggest that a compromise between ABs and ARGs removal must be achieved in order to optimize wastewater treatment processes.

Concomitant inactivation of Acanthamoeba spp. and Escherichia coli using suspended and immobilized TiO2.

This work reports the application of photocatalytic disinfection to the inactivation of Acanthamoeba trophozoites, a free-living pathogenic amoeba. Two types of photocatalytic reactors configurations have been used: i) a slurry reactor using suspended titanium dioxide (TiO2); and, ii) a fixed-bed reactor using immobilized TiO2 onto glass Raschig rings. The effect of the chemical composition of water has been analysed, comparing the efficiency of the process in deionized water (DW) and synthetic wastewater treatment plant effluent (SWTPE). The inactivation of Acanthamoeba spp. has been compared to that of Escherichia coli bacteria, being also analysed the concomitant inactivation of both microorganisms. Our results show that 99% of inactivation of E. coli and Acanthamoeba spp. can be achieved using photocatalysis in both reactor configurations, but interestingly, the kinetics of inactivation of both microorganisms together differs from that found with them separately. Particularly, E. coli seems to be more resistant to the inactivation in the presence of Acanthamoeba spp. which has been justified by the screen effect caused by the bigger size of Acanthamoeba spp. This observation is more pronounced in DW as the composition of the SWTPE prevent the microorganisms from suffering osmotic and/or mechanical stress and protect cellular structures to the attack of reactive oxygen species (ROS). On the other hand, the difference between the inactivation rate of E. coli and Acanthamoeba, points out the importance of the different inactivation mechanisms, suggesting that the entry of small TiO2 particles into the cytoplasm of the Acanthamoeba cells provokes the attack of inner structures and as a consequence a faster inactivation. This mechanism is not possible when the catalyst is immobilized leading to a higher cell resistance to inactivation and consequently lower efficiency of the disinfection process.

Novel antimicrobial agents as alternative to chlorine with potential applications in the fruit and vegetable processing industry.

There has been an increasing demand for fresh fruit and vegetables in recent years. Along the processing line in fresh-cut vegetable production, disinfection is one of the most important processing steps affecting the quality and safety, and the shelf-life of the end produce. Although a range of antimicrobial compounds commonly termed biocides or disinfectants are available, chlorine has long been used to disinfect washing waters of fresh-cut vegetables. However, since chlorine reactions with organic matter lead to the production of by-products, alternative disinfectants to chlorine must be evaluated. A synthetic washing water formula has been developed to determine the antimicrobial efficiency of different families of potential disinfectants: quaternary ammonium compounds (QACs) as benzalkonium chloride (BZK), and didecyldimethylammonium chloride (DDAC); isothiazolinones (mixture of methylchloroisothiazolinone and methylisothiazolinone, CMIT:MIT 3:1 and 1:1); and essential oils (carvacrol, CAR). The twin configuration and higher length of the chains of alkyl groups of DDAC compared to BZK have led to a higher antimicrobial efficiency. In both cases, Gram-positive bacteria seemed to be much more sensitive to the QAC attack than Gram-negative. The opposite happened for CMIT:MIT. The chloro-substituted isothiazolinone (CMIT) has been proven to be much more effective than its unsubstituted form (MIT). In addition, in contrast to chlorine, its antimicrobial activity together with that of DDAC was not decreased when increasing the organic matter content of the water. Synergetic antimicrobial effects have been confirmed when combining BZK and CAR. MBC values were determined in SWW, during 90 s of contact time and Salmonella concentration of 103 CFU/mL, corresponding to: 100 (BZK), 30 (DDAC), 50 (CMIT:MIT 3:1), 100 (CMIT:MIT 1:1), 300 (CAR), 75 (BZK)-200 (CAR), and 9 (free chlorine) mg/L. MBC values for inactivating similar concentration of E. faecalis corresponded to: 50 (BZK), and 10 (DDAC) mg/L. Increasing contact times up to 5 min did not lead to higher antimicrobial efficiencies. CMIT:MIT 3:1 together with DDAC, and combinations of BZK-CAR seem to be a plausible alternative to chlorine.

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.

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.

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.

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.

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.

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.

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.