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

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.

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

From green to clean: options for phytoremediation and phytoextraction of organic pollutants

Jean-Paul Schwitzguebel

The use of green plants specifically chosen or tailored for the remediation of polluted soils and brownfields, the treatment of industrial wastewater or the removal of volatile organic compounds from indoor or outdoor air is becoming essential for sustainable development. Phytoremediation options are less expensive compared to physico-chemical approaches, even if the time scale required reaching the target end-points can be a limiting factor. Phytotechnologies are now offering efficient tools and environmentally friendly solutions for the cleanup of soils and water contaminated by organic pollutants. However this goal requires a sound understanding of how plants can specifically accumulate, detoxify and metabolise xenobiotic compounds. Significant progress has been made recently to better understand the soil, rhizosphere and plant mechanisms involved in the phytotreatment of organic pollutants; to implement phytoextraction, phytodegradation, rhizofiltration, and rhizodegradation as instruments for the removal and/or management of organic contaminants present in soil and water; and to identify critical points in overcoming bottlenecks in plant removal and detoxification of xenobiotics. Depending on the physico-chemical properties of the organic pollutant to be removed or detoxified, as well as on the specific plant physiology and biochemistry, different phytotreatments are available to decontaminate water and soils. For example, aquatic macrophytes or even terrestrial plants can be grown under hydroponic conditions or in constructed wetlands to remove many xenobiotic compounds, e.g. sulphonated anthraquinones and azo dyes present in wastewater from the dye and textile industries. Advances have also been made to remediate soils contaminated with hydrophobic compounds like PCBs, petroleum hydrocarbons or pesticides (e.g. lindane or DDT), highlighting the respective roles of plants, endophytic and rhizospheric bacteria, and the importance of their interactions. These examples illustrate the potential of plants for the phytotreatment of xenobiotics, as well as their ability to cooperate with microorganisms (phytostimulation). Exploring and exploiting the biological diversity of plant metabolism is necessary. Consideration of plant taxonomy and phytochemistry should be the first steps in the appropriate use of the huge potential of plant species, since plants often produce natural chemicals whose structure is close to foreign compounds. Finally, the success of phytoremediation also largely depends on the ability of plants to tolerate the pollutant(s) to be removed. The possible effects of these contaminants on plant physiology and biochemistry must be addressed, since they will determine the ability of a specific plant to deal with specific pollutants or a mixture of them, and thus affect the efficiency of any phytotreatment. It is thus of utmost importance to determine the maximal possible amount of the xenobiotic compounds that can be accumulated and detoxified without injury, critical stress and disruption of metabolism or redox processes in the plant species under consideration. Such information will help to maintain the plant wellness, a key factor to correctly design and size the constructed wetland to remove the foreign compounds present in a particular wastewater or to estimate the time required to clean up a contaminated soil.

2010

Recyclage des eaux usées en irrigation

Yeli Mariam Sou

EPFL2009

From green to clean: options for phytoremediation and phytoextraction of organic pollutants

Jean-Paul Schwitzguebel

2010