Effect of Fe(II)/Fe(III) species, pH, irradiance and bacterial presence on viral inactivation in wastewater by the photo-Fenton process: Kinetic modeling and mechanistic interpretation

Advanced Oxidation Processes and in particular photo-Fenton, represent promising strategies of pathogen inactivation in wastewater effluents. Nevertheless, its full potential is not yet unlocked, as the efficacy of photo-Fenton against viruses has not been deeply explored. In this work, we characterize the effect of major parameters (Fe species and concentration, solar irradiance, pH and microbial competition) on the inactivation of MS2 Coliphage by the photo-Fenton process. The use of Fe(II) salts, under any combination of H2O2 concentration, sunlight irradiance or starting pH (6–8), induced a faster inactivation compared to their Fe(III) counterparts. Moreover, ICP-MS analyses revealed that starting with Fe(II) resulted to higher amount of iron in solution longer than Fe(III), which led to higher inactivation kinetics. Even so, a 4-log MS2 inactivation was achieved upon exposure to 600 W/m2 for 30 min in presence of Fe(III) and H2O2 (1:1 ratio). Furthermore, the inactivation of MS2 was only slightly decreased in presence of the bacterial host, suggesting a low competition for the oxidants in the bulk. The enhancement of iron solubilization through its complexation by organic matter present in wastewater was also investigated, observing an efficient viral inactivation despite the presence of reactive oxygen species (ROS) scavengers. The present data have been used to propose a simple model describing MS2 photo-Fenton inactivation in wastewater. Finally, the pathway describing the photo-Fenton-induced MS2 inactivation in wastewater was proposed, in presence or absence of bacteria.

Enhancing the photo-Fenton treatment of contaminated water by use of ultrasound and iron-complexing agents

Stefanos Papoutsakis

The photo-Fenton process is a promising emerging technology for the treatment of contaminated water streams. It is based on the generation of reactive oxygen species that are capable of destroying recalcitrant contaminants otherwise unaffected by conventional municipal wastewater treatment method. Among its innate advantages are that it can be catalyzed naturally by solar radiation and the main reagents required are iron and hydrogen peroxide, both abundant and relatively cheap. There are however some important limitations. The process functions best at acidic pH, is negatively affected by some inorganic ions present in natural water and the water requires pH neutralization and iron recuperation following the treatment. These limitations inhibit the application of the process at larger-scale. This work is an attempt to develop new strategies for enhancing the photo-Fenton process for making it a more attractive option for the treatment of municipal or industrial wastewaters. Two main pathways are investigated, the use of ultrasound and the use of iron-complexing agents. Ultrasonic processes have been shown to improve degradation kinetics when applied in combination with photo-Fenton, while at the same time are not as negatively affected by some of the inorganic ions present in water. Iron-complexing agents can maintain iron soluble at a wider operational pH and can also improve process efficiency via pathways discussed at length in the text. Chapter 2 is focused on the application of ultrasound in combination with photo-Fenton for two very distinct applications: 1) A pilot-scale ultrasound/photo-Fenton system was set-up and evaluated for the treatment of three different contaminants with distinct physicochemical properties and at different concentrations. Synergy was evaluated in terms of degradation kinetics and H2O2 consumption efficiency. 2) Ultrasound was applied alone and in combination with photo-Fenton for the treatment of the iodinated contrast agent Iohexol. These agents are injected in patients during radiographic procedures and excreted via urine. This provided an opportunity to examine if ultrasound could improve their treatment in such a complex aquatic medium. Treatment options both in urine (at the source) and in the context of municipal wastewater are discussed. Chapter 3 is focused on the use of EDDS as an iron-complexing agent for degrading contaminants at near neutral pH across a concentration range usually found in different wastewaters (from ÎŒg L-1 to mg L-1 ). EDDS was used both for the treatment of microcontaminants (ÎŒg L-1) in municipal wastewater treatment plant effluents as well as for highly contaminated ( several mg L-1) water. The importance of several factors and operational conditions is discussed. Chapter 4 discusses the possibility of exploiting natural iron-complexing agents (mainly phenolic/polyphenolic compounds) that can be found in some types of wastewater (e.g from natural products processing industries). The concept of reusing polyphenol-rich wastewater in small quantities as an alternative to artificial complexing agents is introduced. As a case study, water containing highly concentrated cork bark extracts (Cork Boiling Wastewater) has been added in natural water spiked with one or several contaminants. Its capacity to maintain Fe3+ soluble at near-neutral pH as well as the effect on Fenton/photo-Fenton degradation were observed.

EPFL2016

Recyclage des eaux usées en irrigation

Yeli Mariam Sou

The present study takes place in Ouagadougou (Burkina Faso), a typical Sub-Saharan city where water shortage and food crisis necessitate wastewater reuse in urban agriculture. Different issues linked to this practice were studied in two components separated in two experimental sites. The first part treats about agronomic and sanitary aspects and take place in the 2iE (International Institute for Water and Environmental Engineering) experimental site of Ouagadougou. The second component was emphasised on industrial effluents impacts on irrigated soil quality and takes place in Kossodo, an industrial suburb of Ouagadougou. The 2iE site is supply with treated wastewater from domestic origin. The effluent was used to realise the following objectives: (1) managed wastewater fertilizers to fit the plant needs; (2) assess different crops sanitary quality and the effectiveness of methods used for this assessment. Three treatments were tested: (i) irrigation with the treated wastewater (ii) irrigation with the treated wastewater and fertilizers management, adjusted to plant needs and (iii) conventional treatment i.e. fresh water irrigation and total doses of commercial fertilizers. Each treatment was tested on three different crops: lettuce (Lactuca sativa), carrot (Daucus carota) and eggplant (Solanum melongena). The first objective was achieved by comparing crops yields (on basis of wet and dry matter) obtained with the different treatments. The three crops, irrigated with only wastewater, led to yield reduction between the first and the second year. At the contrary, the adjusted treatment showed higher yield for lettuce, with comparable values to conventional treatment yield. However, the effects on carrot and eggplant did not demonstrate better results; indicating that further investigations must be completed for crops with longer growing periods. Most likely, the fertilizers management should better correspond to the crop period demand. The sanitary assessment (second objective) was performed by measuring the heavy metals concentration (Cd, Cu, Pb, Ni, Cr) and the faecal levels (faecal coliform, Escherichia coli and four pathogens among which Salmonella typhimirium and Vibrio cholerae). Chromocult Coliform Agar medium was used for simultaneous detection of faecal coliform and Escherichia coli whereas pathogens were analysed by Polymerase Chain Reaction (PCR). From methodological point of view, faecal coliform were not sufficiently discriminatory in the case of this study since they were naturally present in the soil as well as in the fresh water. At the contrary, Escherichia coli were better linked to wastewater contamination. However, some "false positive" results were detected meaning that each presumptive colony of Escherichia coli must be confirmed. Nevertheless, microbial quality assessment indicated no Escherichia coli on edible parts of carrot or eggplant irrigated with wastewater. Carrots were expected to have the poorest microbiological quality. Therefore carrot root bacterial quality must be further examined. Results on eggplant are not surprising as these vegetables are somewhat far from the ground and they receive significant solar radiation which acts like a disinfectant. Lettuce from wastewater treatment plots, however, exhibited presence of Escherichia coli, meaning that lettuce is likely to be contaminated by pathogens. However, no pathogens were detected neither on crops irrigated with fresh water nor on those irrigated with wastewater. Heavy metals results demonstrated that the crop's consumption did not involve higher risk for consumers when the vegetables were irrigated with domestic wastewater, in comparison with fresh water irrigation. Kossodo treatment plant receives mainly industrial wastewater, which are characterized by high levels of sodium and bicarbonates. The treated wastewater supplies a market garden in which space has been defined for the study of this second component. The main objective was to assess the impact of treated wastewater on soil quality during two years of irrigation. Early in the second year, the presence of black spots, suspected to be black alkali (dissolved organic matter), appeared at the surface of plots irrigated with treated wastewater. These indications led to put forward the hypothesis of alkalinisation/sodisation on soil receiving wastewater. The methodological approach used was based on in situ measurement of infiltration at the end of the second year of irrigation, supplemented by shrinkage curve modelling and chemical analysis. The hypothesis of an alkalinization/sodisation and dissolved organic matter (black alkali) presence in plots irrigated with treated wastewater were validated by the chemical analysis. Shrinkage curve modelling showed a reduction of the structural porosity on wastewater irrigated plots. The reduction was more marked in the subsurface horizons than in surface, which is probably caused by dispersed clay leached in depth. These structural changes were confirmed in situ by an infiltration capacity greatly reduced on plots irrigated with treated wastewater, compared to control plots (irrigated with fresh water) where the infiltration capacity is higher and comparable to that of non-irrigated soil. The study confirmed the fertilizing value of domestic wastewater while emphasizing the need to concentrate future investigations on sustainable effluent/fertilizers management. The sanitary assessment with different crops regarding their respective distances to the soil was very useful since it showed the strong interaction of soil microbial community on the crop microbial quality. It also revealed the importance to determine a faecal indicator for the crop, specifically related to wastewater contamination. Soil quality assessment reiterated the necessity to verify wastewater quality before its reuse in agriculture. In the case of this study, the sodic and alkaline properties of the industrial effluents make them definitively unfit for irrigation.

EPFL2009

Bacterial Resource Management for Nutrient Removal in Aerobic Granular Sludge Wastewater Treatment Systems

David Gregory Weissbrodt

The approach of wastewater treatment has shifted towards a holistic view in order to achieve sustainability in addition to environmental protection. The aerobic granular sludge (AGS) technology, which relies on the use of fast-settling granular biofilms called granules, is progressively becoming a new standard for high-rate biological nutrient removal (BNR) and secondary clarification in single sequencing batch reactors (SBR). The AGS intensive process has been related with definite savings in land area, construction, and operation costs. In an economical analysis, theoretical savings of CHF 0.45 per m3 (1 Swiss franc CHF ≈ 0.83 €) were computed for a Swiss wastewater treatment plant (WWTP) of 200’000 capita removing all nutrients biologically. Besides scale-up, fundamental research was required to understand and tailor the structure of underlying bacterial communities that form granules and remove nutrients. Mechanisms of bacterial selection were investigated in a systems approach to propose strategic axes for optimal management of the bacterial resource for efficient process performances. This research led to the following advances. After having designed a flexible reactor infrastructure for AGS research, a mathematical modeling methodology was developed to understand the hydraulic and biological processes involved during plug-flow transport of wastewater across the settled AGS bed during the feeding phase. BNR relies on the preferential selection of polyphosphate-accumulating organisms (PAO) by proper uncoupled supply of electron donors and electron acceptors. A bed height to diameter ratio of 6 was deduced to be optimal for full bed loading and efficient anaerobic acetate uptake under reference simulation conditions (20°C, pH 7.0). A bioinformatics methodology called PyroTRF-ID was developed for the identification of bacterial relatives involved in BNR processes by combination of terminal-restriction fragment length polymorphism (T-RFLP) and pyrosequencing data. This procedure provided high resolution of bacterial community structures and dynamics of AGS systems. Electrical conductivity and polyphosphatase assays were proposed for rapid and low-cost assessment of the fractions of active PAO and of the dephosphatating potential of activated sludge and granular sludge. Positive linear correlations were obtained between the fraction of PAO, the biomass specific rate of conductivity evolution measured in anaerobic metabolic batch tests, and the polyphosphate-hydrolyzing enzymatic activity of cell extracts. Wash-out conditions used to stimulate granule formation were shown to exert a selection pressure not only on physical properties of early-stage granules, but also on the underlying bacterial community composition. Operation with constant volumetric organic loading rates (OLR) during wash-out resulted in the formation of slow-settling fluffy granules dominated by filamentous Burkholderiales affiliates formed under low aeration (< 2 cm s-1) and high mesophilic temperature (30°C), and of fast-settling dense granules dominated by Zoogloea spp. under high aeration (4 cm s-1) and with an inoculum originating from a BNR-WWTP. These exopolysaccharide producers were considered as model organisms for granulation. However, their proliferation over PAO and nitrifiers correlated with poor BNR. PAO estab-lished at mature stage as soon as sufficient AGS was present to fully remove volatile fatty acids (VFA) during the anaerobic feeding phase. Without purge of excess sludge, glycogen-accumulating organisms (GAO) competed with PAO at a later stage of reactor operation. Granulation was shown to occur in stirred-tank SBRs operated under steady-state condi¬tions to cultivate PAO and GAO enrichments. The Accumulibacter- and Competibacter-dominated communities displayed granulation potential without involvement of Zoogloea spp. Fast-settling nuclei formed despite initial operation with a settling time as high as 60 min, and evolved towards granules after decrease of settling time to 10 min. Dynamic control of the OLR, anaerobic contact time, and sludge retention time (SRT) selected for active PAO in early-stage granules. Confocal laser scanning microscopy (CLSM) revealed that granula¬tion mechanisms depend on the predominant organisms involved. Fast-growing Zoogloea spp. formed smooth biofilm continuum matrices. The slower-growing PAO and GAO formed het¬erogeneous granular structures by proliferation in compact colonies around flocs. Fluctuations in operation variables were shown by multivariate statistics to impact on process performance and bacterial community structures in anaerobic-aerobic AGS-SBRs. The size of granules impacted on nitrification and dephosphatation by affecting oxygen mass transfer. Efficient BNR was obtained with at least 500 mgCOD L-1of acetate, 30 gCOD gP-1, and 10 gCOD gN-1. Although clades of PAO can denitrify, nitrogen removal was thus not restricted only to PAO. A broad denitrifying community was identified. The bacterial community continuum comprised two major opponent clusters, composed of members of the core microbiome of full-scale BNR-WWTPs. The first mainly comprised Accumulibacter, Nitrospira, Xanthomonadaceae, and Aminobacter affiliates selected by conditions of efficient BNR. The second mainly comprised Competibacter, Sphingobacteriales, Cytophaga, and Tetrasphaera affiliates correlating with periods of low BNR. Bacterial selection in AGS systems was mainly impacted by pH, according to multifactorial experiments. Accumulibacter and BNR were favored with alkaline pH, low mesophilic temperatures, and in the presence of propionate. Competibacter proliferated with acidic pH, temperature close to 30°C, and only acetate. Tetrasphaera spp., potential major PAO of certain full-scale plants, withstood Competibacter-selective conditions. Enhanced BNR was obtained under non-limiting conditions with food-to-microorganism ratios above 25 mgCODs gCODx-1. With fixed 2-h starvation, dephosphatation was only complete with full aeration. Since alternating aerobic-anoxic starvation conditions led to partial conversions, the length of starvation phases should be controlled in function of the redox conditions applied. Overall, optimal bacterial resource management in AGS systems requires full control of system behavior by taking advantage of the flexibility of the SBR technology. A methodology is proposed to this end, comprising milestones for wastewater characterization, SBR design, “anaerobic selector” design, control of the starvation phase length, shaving of fluctuations in operation variables, purge of excess sludge, proper selection for a stable, active and cooperative bacterial community, as well as efficient BNR. As key research perspective, investigations with real wastewater should validate the knowledge gained on bacterial behaviors under low-complexity conditions. Significant differences in predominant bacterial relatives were detected between lab-scale and full-scale BNR sludge. Metagenomics will provide a broader view on key organisms and functions of BNR and AGS microbiomes.

EPFL2013