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Combination of Advanced Oxidation Processes with Biological Treatment

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Combination of Advanced Oxidation Processes with Biological Treatment -Combination of Advanced Oxidation Processes with biological treatment for the remediation of water polluted with herbicides- Memòria presentada per na MªJosé Farré Olalla a l´ Escola de Doctorat i Formació Continuada i al Departament de Química de la Universitat Autònoma de Barcelona, per optar al Grau de Doctora en Química. Univesitat Autònoma de Barcelona Bellaterra, June 2007 Dr. José Peral Pérez Professor Titular del Departament Química de la Universitat Autònoma de Barcelona, CERTIFICO: Que la Llicenciada en Química MªJosé Farré Olalla ha realitzat la tesis titulada “Combination of Advanced Oxidation Processes with biological treatment for the remediation of water polluted with herbicides” al Departament de Química de la Universitat Autònoma de Barcelona sota la meva direcció per optar al grau de Doctora en Química. I per que així consti, signo el present certificat a Bellaterra el 13 de abril del 2007. José Peral Pérez INDEX Acknowledgements Foreword Glossary of symbols and abbreviations Table of contents 1. INTRODUCTION 2. MATERIALS AND METHODS 3. RESULTS AND DISCUSSION 4. CONCLUDING REMARKS Unpublished results Additional information Acknowledgments This work has been supported by European Commission (CADOX project, EVK1-CT-2002- 00122), Spanish Government (MEC, project CTQ2005-02808) and CICYT (project PPQ2002- 04060-C02-01). I also want to thank Makhteshim Agan España S.A., Aragonesas Agro S.A and the WWTP from Manresa. I would like to express gratitude to the Green Chemistry and Photocatalysis group from the Universitat Autònoma de Barcelona for giving me the opportunity to carry out a doctoral project. In particular, I would like to thank my thesis director Dr. José Peral for the supervision, attention and help received. I also want to thank particularly Dr. Xavier Domènech in recognition of his effort to achieve a “sustainable environment” of work in the group, beyond the knowledge and experience shown. In addition, I am grateful to Dr. Stephan Brosillon for accepting and guiding me during my stay at l´ Ecole Nationale Supérieure de Chimie de Rennes. Moreover, I would like to thank Dr. José Antonio Ayllón and Dr. Julián Carrera for their help with the revision of some parts of the final manuscript. Also I thank Dra. Alba Eustaquio for the chromatography lessons received and Albert Guisasola for the respirometry assessment. Last but not least, I owe big thanks to Julia García for her continuous aid, for introducing me to SBR technology and biological analyses as well as, in collaboration with Dr. Ivan Muñoz and Nilbia Ruiz, for their help with the LCA studies presented in this thesis. I would also express thanks to; Dra. Maribel Franch, David Gutiérrez, Ana Serra, Marc Estruga, Marc Campillo, Dani Calvo, Juan Manuel Ramírez, Xavi Batlle, Neus Vilà, Meritxell Bartés, Nuria Crivillers, Raquel Rios, Noemí Parraga and other colleagues that have been close to me inside this “green world” during these four years for their help, patience and support. A particular thank is to Rosa Calzada for making easier and funnier the bureaucratic stuff. Finally, a very special “thank you” goes to my family and friends for being there whenever I need them. Among them, I want to especially thank Cristian. MªJosé To my parents and my sister… Why do they want the scarecrow if we are scared enough with their herbicides….. Foreword Water is an irreplaceable basic principle for life. This natural resource is a factor of subsistence for the human beings as well as a fundamental element for social welfare. Nevertheless, although water is one of the most abundant resources on the planet, still 1100 million people (i.e., 18% of the world’s population) have no access to safe drinking water and 2600 million people (i.e., 42% of the world’s population) have no access to improved sanitation. The main reason is that 97.5% of the water in the planet is located in the sea; therefore it is excessively salty for direct use as drinking water. 70% of the remaining 2.5%, that is fresh water, is locked in the icecaps and glaciers. 20% is confined to remote areas, and much of the rest arrives at the wrong time and place causing natural disasters. Thus, only less than 1% of the world’s fresh water resources are ready for human use. The problem with regard to the water requirement is not only related to its supply, but also to its demand. Globally, domestic use represents 10% of the world’s fresh water ready for human use. This demand is estimated to increase about 50% in the next two decades, mainly due to the predicted growth in the global population from 6500 million today to 7900 million by 2025. Apart from the domestic needs, the local requirement is divided mainly into industrial and agricultural demand. Industrial water use represents 20% of the world’s fresh water ready for human use. In this ever-increasing sector, the water cycles are generally open. The industry extracts water from aquifers, from surface water or the public drinking water net and then, after being used for industrial needs, it is discharged as wastewater. On the other hand, water required for agriculture, which corresponds to the highest percentage of world’s fresh water ready for human use (i.e., 66%), is increasing even faster. This rise is mainly due to extensive irrigation programmes necessary to fulfil the increasing population’s needs and to sustain the industrial agriculture of the “Green Revolution”. Apart from that, 4% of the world’s fresh water is evaporated directly from reservoirs. The water quality is the last but not least factor to consider when discussing water shortage. The non-biodegradable anthropogenic pollution discharged in the water systems deteriorates the water quality and, consequently, the removal of pollutants at source is of imminent necessity. Due to all the aspects mentioned, water shortage is one of the most worrying problems for this millennium. “Reducing by half the proportion of people without sustainable access to safe drinking water” as well as “integrate the principles of sustainable development into country policies and programmes and reverse loss of environmental resources” are part of the 7th UN millennium development goal. The unbalanced ratio between water supply and water demand, as well as the water quality deterioration, mean it is important to develop new operating systems that guarantee the optimization of the use of this natural resource. One particular proposition to reach equilibrium is to relieve the water shortage by utilizing regenerated wastewaters. Regenerated wastewater is water that after being used is treated and disinfected for subsequent re-use. As mentioned above, the industry sector uses approximately 20% of the total water ready for human use, most of it is used in cooling, washing or rinsing processes. In those cases, the utilization of regenerated wastewater is highly relevant. Regenerated wastewater can be also an attractive proposition for agricultural water necessities. Both, the industrial and agricultural optimization of water, could contribute to the improvement of the environmental quality as well as to the improvement of public water supply. One example of innovative technology to regenerate wastewater is the so- called Advanced Oxidation Processes (AOP) which can be optimised by combining with biological treatments. The aim of this work is to bring new insights into the general problem of water quality improvement by finding new ways of treating water polluted with different herbicides. The work has been divided in four chapters: Introduction, Materials and Methods, Results and Discussion and Concluding Remarks. The Introduction reviews and describes the Advanced Oxidation Processes used in this work, the biological treatment, the natural interferences found in wastewater, and some different strategies used to assess the efficiency of the coupling of chemical and biological treatments. In addition, the environmental impacts associated to this strategy have been evaluated by means of Life Cycle Assessment methodology. Thus, a brief introduction to this environmental assessment tool has been also included. The Materials and Methods chapter has been added to the memory in order to facilitate repetition of the methods and guide further work in this field, as well as to allow the reader to understand all the experiments carried out. The Results and Discussion chapter is presented as a compendium of four publications. Degradation of some biorecalcitrant pesticides by homogeneous and heterogeneous photocatalytic ozonation Chemosphere 58 (2005) 1127-1133. Biodegradability of treated aqueous solutions of biorecalcitrant pesticides by means of photocatalytic ozonation Desalination 211 (2007) 22-33. Assessment of photo-Fenton and biological treatment coupling for Diuron and Linuron removal from water Water Research 40 (2006) 2533-2540. Combined photo-Fenton and biological treatment for Diuron and Linuron removal from water containing humic acid Journal of Hazardous Materials in press. Two more works accepted for publication are included in Annexe 1. Evaluation of the intermediates generated during the degradation of Diuron and Linuron herbicides by the photo-Fenton reaction Accepted for publication in Journal of Photochemistry and Photobiology A: Chemistry. Life cycle assessment for the removal of Diuron and Linuron herbicides from water using three environmental friendly technologies Accepted for publication in Environmental Technology. The theoretical framework, the methods used, as well as the results
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