Stefanos Giannakis

Ultrasound enhancement of near-neutral photo-Fenton for effective E. coli inactivation in wastewater

In this study, we attempt for the first time to couple sonication and photo-Fenton for bacterial inactivation of secondary treated effluent. Synthetic wastewater was subjected to sequential high-frequency/low power sonication, followed by mild photo-Fenton treatment, under a solar simulator. It was followed by the assessment of the contribution of each component of the process (Fenton, US, hv) towards the removal rate and the long-term survival; sunlight greatly improved the treatment efficiency, with the coupled process being the only one to yield total inactivation within the 4-h period of treatment. The short-term beneficial disinfecting action of US and its detrimental effect on bacterial survival in long term, as well as the impact of light addition were also revealed. Finally, an investigation on the operational parameters of the process was performed, to investigate possible improvement and/or limitations of the coupled treatment; 3 levels of each parameter involved (hydraulic, environmental, US and Fenton) were tested. Only H2O2 increased improved the process significantly, but the action mode of the joint process indicated potential cost-effective solutions towards the implementation of this method.

Iron oxide-mediated semiconductor photocatalysis vs. heterogeneous photo-Fenton treatment of viruses in wastewater. Impact of the oxide particle size

The photo-Fenton process is recognized as a promising technique towards microorganism disinfection in wastewater, but its efficiency is hampered at near-neutral pH operating values. In this work, we overcome these obstacles by using the heterogeneous photo-Fenton process as the default disinfecting technique, targeting MS2 coliphage in wastewater. The use of low concentrations of iron oxides in wastewater without H2O2 (wüstite, maghemite, magnetite) has demonstrated limited semiconductor-mediated MS2 inactivation. Changing the operational pH and the size of the oxide particles indicated that the isoelectric point of the iron oxides and the active surface area are crucial in the success of the process, and the possible underlying mechanisms are investigated. Furthermore, the addition of low amounts of Fe-oxides (1mgL-1) and H2O2 in the system (1, 5 and 10mgL-1) greatly enhanced the inactivation process, leading to heterogeneous photo-Fenton processes on the surface of the magnetically separable oxides used. Additionally, photo-dissolution of iron in the bulk, lead to homogeneous photo-Fenton, further aided by the complexation by the dissolved organic matter in the solution. Finally, we assess the impact of the presence of the bacterial host and the difference caused by the different iron sources (salts, oxides) and the Fe-oxide size (normal, nano-sized).

Iohexol degradation in wastewater and urine by UV-based Advanced Oxidation Processes (AOPs): Process modeling and by-products identification

In this work, an Iodinated Contrast Medium (ICM), Iohexol, was subjected to treatment by 3 Advanced Oxidation Processes (AOPs) (UV, UV/H2O2, UV/H2O2/Fe2+). Water, wastewater and urine were spiked with Iohexol, in order to investigate the treatment efficiency of AOPs. A tri-level approach has been deployed to assess the UV-based AOPs efficacy. The treatment was heavily influenced by the UV transmittance and the organics content of the matrix, as dilution and acidification improved the degradation but iron/H2O2 increase only moderately. Furthermore, optimization of the treatment conditions, as well as modeling of the degradation was performed, by step-wise constructed quadratic or product models, and determination of the optimal operational regions was achieved through desirability functions. Finally, global chemical parameters (COD, TOC and UV-Vis absorbance) were followed in parallel with specific analyses to elucidate the degradation process of Iohexol by UV-based AOPs. Through HPLC/MS analysis the degradation pathway and the effects the operational parameters were monitored, thus attributing the pathways the respective modifications. The addition of iron in the UV/H2O2 process inflicted additional pathways beneficial for both Iohexol and organics removal from the matrix.

Environmental considerations on solar disinfection of wastewater and the subsequent bacterial (re)growth

In this work, solar disinfection of wastewater was studied, focusing on the effect of selected environmental variables, namely light intensity, continuous/intermittent light delivery, and post-irradiation storage as well as dilution in lake water. These variables were studied for their effect on the disinfection efficiency and on post-irradiation survival/regrowth in undiluted wastewater and in wastewater diluted in lake water at different dilution rates. The bacterial inactivation curves were studied, and distinct kinetic phases were identified and interpreted. The dose primarily influenced the demonstration of phases and total inactivation times, independently of the irradiance. Intermittent illumination unevenly prolonged the required exposure time and highlighted the need for extended illumination times when unstable weather conditions are expected. Post-irradiation survival/regrowth in undiluted wastewater showed three distinct kinetic profiles, with transitions among them largely determined by the applied light dose. Lower doses resulted in similar inactivation profiles to the higher ones, when irradiation was followed by prolonged storage at high dilution rates in lake water. The studied factors show significant design and operation implications for solar wastewater applications based on local environmental conditions and water receptor restrictions.

Light-Assisted Advanced Oxidation Processes for the Elimination of Chemical and Microbiological Pollution of Wastewaters in Developed and Developing Countries

In this work, the issue of hospital and urban wastewater treatment is studied in two different contexts, in Switzerland and in developing countries (Ivory Coast and Colombia). For this purpose, the treatment of municipal wastewater effluents is studied, simulating the developed countries’ context, while cheap and sustainable solutions are proposed for the developing countries, to form a barrier between effluents and receiving water bodies. In order to propose proper methods for each case, the characteristics of the matrices and the targets are described here in detail. In both contexts, the use of Advanced Oxidation Processes (AOPs) is implemented, focusing on UV-based and solar-supported ones, in the respective target areas. A list of emerging contaminants and bacteria are firstly studied to provide operational and engineering details on their removal by AOPs. Fundamental mechanistic insights are also provided on the degradation of the effluent wastewater organic matter. The use of viruses and yeasts as potential model pathogens is also accounted for, treated by the photo-Fenton process. In addition, two pharmaceutically active compound (PhAC) models of hospital and/or industrial origin are studied in wastewater and urine, treated by all accounted AOPs, as a proposed method to effectively control concentrated point-source pollution from hospital wastewaters. Their elimination was modeled and the degradation pathway was elucidated by the use of state-of-the-art analytical techniques. In conclusion, the use of light-supported AOPs was proven to be effective in degrading the respective target and further insights were provided by each application, which could facilitate their divulgation and potential application in the field.

Analogies and differences among bacterial and viral disinfection by the photo-Fenton process at neutral pH: a mini review

Over the last years, the photo-Fenton process has been established as an effective, green alternative to chemical disinfection of waters and wastewaters. Microorganisms’ inactivation is the latest success story in the application of this process at near-neutral pH, albeit without clearly elucidated inactivation mechanisms. In this review, the main pathways of the combined photo-Fenton process against the most frequent pathogen models (Escherichia coli for bacteria and MS2 bacteriophage for viruses) are analyzed. Firstly, the action of solar light is described and the specific inactivation mechanisms in bacteria (internal photo-Fenton) and viruses (genome damage) are presented. The contribution of the external pathways due to the potential presence of organic matter in generating reactive oxygen species (ROS) and their effects on microorganism inactivation are discussed. Afterwards, the effects of the gradual addition of Fe and H2O2 are assessed and the differences among bacterial and viral inactivation are highlighted. As a final step, the simultaneous addition of both reagents induces the photo-Fenton in the bulk, focusing on the differences induced by the homogeneous or heterogeneous fraction of the process and the variation among the two respective targets. This work exploits the accumulated evidence on the mechanisms of bacterial inactivation and the scarce ones towards viral targets, aiming to bridge this knowledge gap and make possible the further application of the photo-Fenton process in the field of water/wastewater treatment.

Light wavelength-dependent E. coli survival changes after simulated solar disinfection of secondary effluent

In this study, the photoreactivation and the modification of dark repair of E. coli in a simulated secondary effluent were investigated after initial irradiation under different conditions. The simulated solar exposure of the secondary wastewater was followed by exposure to six different low-intensity fluorescent lamps (blacklight blue, actinic blacklight, blue, green, yellow and indoor light) for up to 8 h. When photoreactivation was monitored, blue and green colored fluorescent light led to increased bacterial regrowth. Blacklight lamps further inactivated the remaining bacteria, while yellow and indoor light led to accelerated growth of healthy cells. Exposure to fluorescent lamps was followed by long term storage in darkness, to monitor the bacterial repair in the dark. The response was correlated with the pre-exposure dose of applied solar irradiation, and to a lesser extent with the fluorescent light dose. Bacteria which had undergone extensive exposure showed no response under fluorescent light or during storage in the dark. Finally, the statistical treatment of the data allowed us to suggest a linear model, which is non-selective in terms of the fluorescent light applied. The estimation of the final bacterial population was predicted well (R-sq ∼ 75%) and the photoreactivation risk was found to be more important for cultivable cells.

Self-Sterilizing Sputtered Films for Applications in Hospital Facilities

This review addresses the preparation of antibacterial 2D textile and thin polymer films and 3D surfaces like catheters for applications in hospital and health care facilities. The sputtering of films applying different levels of energy led to the deposition of metal/oxide/composite/films showing differentiated antibacterial kinetics and surface microstructure. The optimization of the film composition in regards to the antibacterial active component was carried out in each case to attain the fastest antibacterial kinetics, since this is essential when designing films avoiding biofilm formation (under light and in the dark). The antimicrobial performance of these sputtered films on Staphylococcus aureus (MRSA) and Escherichia coli (E. coli) were tested. A protecting effect of TiO2 was found for the release of Cu by the TiO2-Cu films compared to films sputtered by Cu only. The Cu-released during bacterial inactivation by TiO2-Cu was observed to be much lower compared to the films sputtered only by Cu. The FeOx-TiO2-PE films induced E. coli inactivation under solar or under visible light with a similar inactivation kinetics, confirming the predominant role of FeOx in these composite films. By up-to-date surface science techniques were used to characterize the surface properties of the sputtered films. A mechanism of bacteria inactivation is suggested for each particular film consistent with the experimental results found and compared with the literature.

Solar photo-Fenton disinfection of 11 antibiotic-resistant bacteria (ARB) and elimination of representative AR genes. Evidence that antibiotic resistance does not imply resistance to oxidative treatment

The emergence of antibiotic resistance represents a major threat to human health. In this work we investigated the elimination of antibiotic resistant bacteria (ARB) by solar light and solar photo-Fenton processes. As such, we have designed an experimental plan in which several bacterial strains (Staphylococcus aureus, Escherichia coli and Klebsiella pneumoniae) possessing different drug-susceptible and -resistant patterns and structures (Gram-positive and Gram-negative) were subjected to solar light and the photo-Fenton oxidative treatment in water. We showed that both solar light and solar photo-Fenton processes were effective in the elimination of ARB in water and that the time necessary for solar light disinfection and solar photo-Fenton disinfection were similar for antibiotic-susceptible and antibiotic-resistant strains (mostly 180-240 and 90-120 min, respectively). Moreover, the bacterial structure did not significantly affect the effectiveness of the treatment. Similar regrowth pattern was observed (compared to the susceptible strain) and no development of bacteria with higher drug-resistance values was found in waters after any treatment. Finally, both processes were effective to reduce AR genes (ARGs), although solar photo-Fenton was more rapid than solar light. In conclusion, the solar photo-Fenton process ensured effective disinfection of ARB and elimination of ARGs in water (or wastewater) and is a potential mean to ensure limitation of ARB and ARG spread in nature.

Effect of μM Fe addition, mild heat and solar UV on sulfate radical-mediated inactivation of bacteria, viruses, and micropollutant degradation in water

In this work, solar disinfection (SODIS) was enhanced by moderate addition of Fe and sodium peroxydisulfate (PDS), under solar light. A systematic assessment of the activating factors was performed, firstly isolated, then in pairs and concluded in the combined Fe/heat/solar UV-PDS activation process. Solar light was the most effective (single) activator, and its combination with Fe and heat (double activation) yielded high level of synergies (up to S = 2.13). The triple activation was able to reduce the bacterial load up to 6-log in less than 1 h, similarly to the photo-Fenton process done in comparison (SODIS alone: >5 h). Fe-oxides were suitable activators of PDS under the same conditions while the presence of organic matter enhanced bacterial inactivation by the triple activated PDS process. The degradation of a (selected) mixture of micropollutants (i.e. drugs, pesticides) was also achieved in similar order of magnitude, and faster than the photo-Fenton process. Finally, the removal of a viral pathogen indicator (MS2 bacteriophage) was attained at minute-range residence times. The aforementioned facts indicate the suitability of the mild, combined process, as a potential SODIS enhancement, producing safe drinking water for sunny and especially for developing countries.