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.

Impacts of irrigation with industrial treated wastewater on soil properties

Pascal Boivin, André Mermoud

Wastewater reuse in agriculture is a widespread practice in developing countries, especially in urban areas where water shortage and poverty encourage people to use that marginal resource. Raw or treated wastewaters are used by farmers, but even treated wastewaters frequently do not meet WHO and FAO standards for irrigation water. Such practices may lead to health hazards, relatively well documented in the literature and to environmental damages. Adverse environmental impacts such as soil degradation and groundwater contamination are frequently associated with the use of wastewater from industrial sources. Previous studies have demonstrated that wastewater irrigation may decrease soil hydraulic conductivity and infiltration rate. Nevertheless, the effects on soil structural and chemical behaviors have been little studied so far and need further investigations. The impacts of irrigation with alkaline and sodic industrial wastewater previously treated in microphyte ponds on soil physical and chemical properties were studied downstream the sewage treatment plant of Kossodo in Ouagadougou, on plots cropped with eggplants. Plots irrigated with fresh water and non cropped, non irrigated plots were used as controls. Different soil properties were characterized: pore volumes determined by using shrinkage analysis, pH and electrical conductivity of water extracts, and major soluble and exchangeable cations (Ca, Mg, K, and Na). Organic matter characterization was performed by means of three dimensional fluorescence spectra analysis to determine its origin and evolution on irrigated soils. Plots irrigated with wastewater showed important structural damages, especially in the subsurface horizon where the soil pore network collapsed dramatically, resulting in a compact impermeable layer. Fluorescence spectra revealed that the organic matter contained in the wastewater was largely dissolved due to a sharp soil pH increase, resulting in black alkali formation at the surface: the soil became sodic, with an exchange complex dominated by sodium, whereas plots irrigated with fresh water kept properties comparable to that of non irrigated plots. Such a rapid soil sodication was seldom reported so far. The study emphasizes the need to carefully examine irrigation water quality and particularly calcite residual alkalinity and suggests that shrinkage analysis could be used to monitor the physical changes of soil properties upon sodication. Inadequate wastewater quality is likely to cause deep and irreversible damages to irrigated soils. (C) 2013 Elsevier B.V. All rights reserved.

Elsevier Science Bv2013

Origines et flux de biocides et de filtres UV dans les stations d'épuration des eaux usées

Cécile Plagellat

Adverse effects on the environment have become a matter of increasing concern considering the increase of industrialization and of the amount of commercialized chemicals. At present, approximately 100'000 substances are on the market, 3000 are sold at high volumes. In Europe, 200 to 300 new substances are authorized every year (in Switzerland, approximately 50). Contamination is induced by consumption of numerous products frequently applied by private or professional users. Persistence and ecotoxicity of certain organic compounds contained in these products might have impacts on the quality of our environment. Knowledge on potential sources of these substances is the first step in order to limit their release. The project developed within the present PhD thesis aims at determining the sources of certain compounds by applying material flux analysis on the basis of sewage sludge. Presently, a large number of anthropogenic organic compounds originating from private households, craft industry, industry and stormwater is disposed of into the collector system and ends up in sewage sludge. Carbendazim, diuron, Irgarol 1051®, octhilinone, permethrin, tributyltin (TBT) and triphenyltin (TPT) comprise numerous applications as biocides and pesticides whilst methylbenzylidene camphor (4-MBC), octyl methoxy cinnamate (OMC), octocrylene (OC) and octyl triazone (OT) are used as UV-screens (type UVB) in a large number of cosmetic products. Their toxic effects on non-target organisms and their potential for bioaccumulation give rise to environmental concern. These substances are used as ingredients in products of daily use and are disposed of into wastewater. Due to their physico-chemical properties they are more or less lipophilic and are likely to persist in sewage sludge. On the basis of the analysis of sewage sludge samples from well characterized sites (catchments and wastewater treatment plants, WWTPs) it is possible to determine the sources (private households, craft industry, industry and stormwater). The first step of this study was the development of analytical methods which allow for quantification of these compounds in sewage sludge. Due to their different physico-chemical properties, four different methods were required. These methods have recovery rates ranging between 75 and 106 % and limits of detection in the order of μg/kg dry matter. The analysis of sludge from 12 sites obtained within 2 sampling periods show that most of the substances are present in all samples. Mean concentrations were 6,8 μg/kg dm (dry matter) for carbendazim, 9,5 μg/ kg d.m. for diuron, 98,1 μg/kg d.m. for permethrin, 148 μg/kg d.m. for TBT, 1777 μg/kg d.m.for 4-MBC, 110 μg/kg d.m. for OMC, 4834 μg/kg d.m. for OC and 5517 μg/kg d.m. for OT. Octhilinone was not detected whilst Irgarol 1051® and TPT were found in 7 and 11 samples, respectively. The transfer of these compounds from wastewater into sludge is an important parameter for material flux analysis on the basis of sewage sludge. A study on the fate of carbendazime and permethrin during wastewater treatment has been carried out on two WWTPs. Whilst removal of permethrin was high (>94%) up to 70% of carbendazime present in sewage were found in treatment plant effluents. Adsorption is an important process for removal of permethrin. However, only 4 to 15 % of the load in wastewater was transferred to sewage sludge. Carbendazim is mainly associated to the aqueous phase and thus, a very small quantity ends up in sludge (approximately 1%). Therefore, the loads found in sewage sludge are more or less representative for consumption of the compounds in the catchments according to their physico-chemical properties. Additionally, it has been shown that the part of permethrine ending up in sludge depends on the treatment techniques of the WWTPs. Thus, for comparison of the pollutant loads in sewage sludge between different sites their fate in the WWTPs has to be known. The loads per inhabitant of the three well characterized types of sites have been calculated in order to determine the sources of the substances. Type A comprises sites with a separate sewer system and a catchment where mainly private households are present. Type B has a combined sewer system collecting sewage from private households, craft industry and stormwater whilst type C comprises a combined sewer system which includes effluents from private households and industry as well as stormwater. The results are as follows: Stromwater is considered as main source of carbendazim in wastewater whilst diuron originates mainly from stormwater and from industrial effluents. Private households contribute significantly to the loads of permethrine and TBT in sewage. For UV-screens the loads from private households are also important but stormwater and industrial effluents are likely to be potential sources as well. A difference in consumption between rural (type A) and more urban sites (type B and C) is possible which might hamper a proper estimate of the sources of UV-screens.

EPFL2004

Photochemical-biological treatment of a real industrial biorecalcitrant wastewater containing 5-amino-6-methyl-2-benzimidazolone

Sandra Parra Cardona, César Pulgarin, Victor Sarria

5-amino-6-methyl-2-benzimidazolone (AMBI), used in the manufacture of dyes, was characterised as a biorecalcitrant compound by means of different biodegradability tests. In order to enhance the biodegradability of this important pollutant, the application of Advanced Oxidation Process (AOPs) as a pre-treatment was explored. Some experiments were addressed to find the most efficient AOP. The systems H2O2/hv, TiO2/H2O2/hv, Fe3+/hv, Fe3+/H2O2 and Fe3+/H2O2/hv were compared. The photo-Fenton system was the most efficient and the optimal conditions (AMBI, Fe3+, H2O2 concentrations) for the degradation of AMBI were found. During the photo-Fenton degradation, experiments were also made to obtain information concerning the evolution of: (a) organic carbon and initial compound concentration; (b) the oxidation state; (c) the toxicity; (d) the biodegradability; and (e) the chemical nature of the intermediates. These analyses show that the solution resulting from the treatment of AMBI is biologically compatible and complete mineralisation can be performed by biological means. A combined photochemical (Fenton) and biological flow reactor for the degradation of AMBI was successfully operated in continuous mode at laboratory scale. 100% of the initial concentration of AMBI and 80.3% of Dissolved Organic Carbon (DOC) were removed in 3.5 hours of total residence time. Finally, some field experiments under direct sunlight carried out at the Plataforma Solar de Almeria, Spain, demonstrated that this solar catalytic system is an effective treatment for this kind of industrial wastewater.