TREATMENT OF ORGANOPHOSPHORUS INSECTICIDES AND PHENOXYACETIC ACID HERBICIDES USING MEMBRANE BIOREACTOR TECHNOLOGY by AVIK GHOSHDASTIDAR Thesis submitted in partial fulfillment of the requirements for the Degree of Master of Science (Chemistry) Acadia University Spring Convocation 2012 © by AVIK GHOSHDASTIDAR, 2012 This thesis by Avik Ghoshdastidar was defended successfully in an oral examination on April 18, 2012. The examining committee for the thesis was: ________________________ Dr. Rick Mehta, Chair ________________________ Dr. Michael Earle, External Examiner ________________________ Dr. Amitabh Jha, Internal Examiner ________________________ Dr. Anthony Tong, Supervisor _________________________ Dr. John Murimboh, Head This thesis is accepted in its present form by the Division of Research and Graduate Studies as satisfying the thesis requirements for the degree Master of Science (Chemistry) …………………………………………. ii This thesis by Avik Ghoshdastidar was defended successfully in an oral examination on April 18, 2012. The examining committee for the thesis was: Dr. Rick Mehta, Chair Dr. Michael Earle, External Examiner Dr. Amitabh Jha, Internal Examiner Dr. Anthony Tong, Supervisor Dr. John Murimboh, Head This thesis is accepted in its present form by the Division of Research and Graduate Studies as satisfying the thesis requirements for the degree Master of Science (Chemistry) I, Avik Ghoshdastidar, grant permission to the University Librarian at Acadia University to reproduce, loan or distribute copies of my thesis in microform, paper or electronic formats on a non-profit basis. I, however, retain the copyright in my thesis. ______________________________ Avik Ghoshdastidar ______________________________ Dr. Anthony Tong ______________________________ April 18, 2012 iii Table of Contents Table of Contents ......................................................................................................... iv List of Tables .............................................................................................................. viii List of Figures ................................................................................................................ x Abstract ....................................................................................................................... xii List of Abbreviations .................................................................................................. xiii Acknowledgements ................................................................................................... xvii 1 Introduction ............................................................................................................. 1 1.1 Introduction to Pesticides ............................................................................... 1 1.1.1 Definitions .................................................................................................... 1 1.1.2 History of Pesticide Use ............................................................................... 1 1.1.3 Pesticide Usage ............................................................................................ 5 1.1.4 The Economics of Pesticide Use ................................................................. 11 1.1.5 The Chemistry of Organophosphorus Insecticides .................................. 14 1.1.6 The Chemistry of PA and Benzoic Acid Herbicides ................................. 19 1.1.7 PA and Benzoic Acid Metabolites ............................................................ 22 1.1.8 Environmental Exposure and Pesticide Occurrence ............................... 22 1.1.9 Fate of Pesticides in Aquatic Environments ............................................ 28 1.1.10 Pesticide Toxicology .................................................................................. 38 1.1.11 Pesticide Regulations and Legislation ...................................................... 43 1.2 Water Quality ............................................................................................... 45 1.2.1 Physical Properties .................................................................................... 45 1.2.2 Inorganic Non-metallics ........................................................................... 47 1.2.3 Organics ..................................................................................................... 49 1.2.4 Microbiological Examination .................................................................... 50 1.3 Pesticide Treatment ...................................................................................... 50 1.3.1 Conventional Wastewater Treatment ...................................................... 50 1.3.2 Constructed Wetlands ............................................................................... 51 1.3.3 Granular Activated Carbon ....................................................................... 52 1.3.4 Ozonation ................................................................................................... 53 1.3.5 Photocatalytic oxidation ........................................................................... 54 1.3.6 Fenton’s Reagent ....................................................................................... 56 iv 1.3.7 Gamma Irradiation .................................................................................... 59 1.3.8 Ultrasonic Wave Treatment ...................................................................... 59 1.3.9 Bioremediation .......................................................................................... 59 1.3.10 Metabolite Treatment ................................................................................ 61 1.3.11 Pesticide Wastewater Treatment .............................................................. 62 1.4 Membrane Bioreactor ................................................................................... 63 1.4.1 Introduction to Membrane Bioreactor ..................................................... 63 1.4.2 The History of Membrane Bioreactors ..................................................... 65 1.4.3 Membrane Fouling .................................................................................... 66 1.5 Objective ........................................................................................................ 68 2 Materials and Methods .........................................................................................69 2.1 Membrane Bioreactor ...................................................................................69 2.2 Experimental Setup .......................................................................................69 2.2.1 Wastewater Tank .......................................................................................69 2.2.2 Intermediate Tank ...................................................................................... 71 2.2.3 Pesticide Tank ............................................................................................. 71 2.2.4 Peristaltic Pumps and Flow Rates ............................................................. 72 2.2.5 Aeration Spargers ....................................................................................... 72 2.2.6 Temperature Controls ............................................................................... 73 2.2.7 Aeration ...................................................................................................... 73 2.2.8 Sampling ..................................................................................................... 73 2.3 Analytical Methods ....................................................................................... 74 2.3.1 Solid Phase Extraction ............................................................................... 74 2.3.2 Gas Chromatography ................................................................................. 74 2.3.3 High Pressure Liquid Chromatography .................................................... 75 2.3.4 Mass Spectrometry .................................................................................... 75 2.3.5 Quantitation............................................................................................... 75 2.4 Materials and Standards ............................................................................... 75 2.4.1 OP Pesticide Experiment ........................................................................... 75 2.4.2 PA Pesticide Experiment ........................................................................... 77 2.5 Chemical Analysis ......................................................................................... 78 2.5.1 Solid Phase Extraction ............................................................................... 78 2.5.2 Gas Chromatography – Mass Spectrometry ............................................. 79 v 2.5.3 Liquid Chromatography – Mass Spectrometry ........................................ 80 2.5.4 Quality Assurance/Quality Control .......................................................... 81 2.6 Spectrophotometric Analysis ........................................................................ 81 2.7 Potentiometric Analysis ............................................................................... 82 2.7.1 pH ............................................................................................................... 82 2.7.2 Dissolved Oxygen .....................................................................................