Determination of rate constants of low volatile, particle-bound, long-lived,persistent pollutants by OH-radicals

Abstract

Abstract Zusammenfassung 1\. Introduction 1.1 Scientific Background 1.2 The aim of the work 1.3 Methodology 1.4 Outline of this Thesis 2\. Background and methods 2.1 Pesticides in the environment and degradation processes 2.1.1 Transport and degradation processes 2.2 Spectroscopic methods for the detection of pesticides 2.2.1 Classical Raman effect 2.2.1.1 Resonance Raman Spectroscopy 2.2.1.2 Raman microscopy 2.2.2 Mass spectrometry 2.2.3 Nuclear magnetic resonance (NMR) 2.3 Lasers 2.4 Reaction kinetics 2.4.1 Fundamentals of kinetics 2.4.1.1 Reaction monitoring 2.4.1.2 Reaction rate 2.4.1.3 Elementary reactions 2.4.1.4 Order of reaction 2.4.1.5 Zero-order reactions 2.4.1.6 First-order reactions 2.4.1.7 Second-order reactions 2.4.2 Kinetics of surface-bound species 3\. Experimental setup and sample preparation 3.1 Sample preparation 3.1.1 Introduction 3.1.2 Review on laboratory approaches on reactive degradation of pesticides 3.2 Materials 3.3 Production of OH-radicals 3.3.1 Photolysis of O3 in the presence of water vapor 3.3.2 Photolysis of hydrogen peroxide 3.4 Raman Spectroscopy and Microscopy 3.4.1 Calibration procedures 3.4.2 Estimation of error limits 4\. Results and Discussion 4.1. Degradation of terbuthylazine by indirect photooxidation 4.1.1 Monitoring of the OH-radiral concentration 4.1.2 Evaluation of the Raman spectra of TBA 4.1.3 Kinetics analysis of the Raman spectra of TBA 4.1.3.1 Recapitulation: Confidence range of rate constant and for the OH concentration 4.1.3.2 Discussion of the time-dependent behavior of important Raman bands evaluated for the description of TBA indirect photolysis kinetics 4.1.4 Infrared Spectra 4.1.5 Characterization of the reaction products by NMR and mass spectrometry 4.1.5.1 Nuclear magnetic resonance 4.1.5.2 Mass Spectroscopy (MS) 4.2 Degradation of simazine by indirect photo-oxidation 4.2.1 Evaluation of Raman spectra 4.2.2 Kinetics analysis 4.2.3 Characterization of simazine degradation products by NMR and mass spectrometry 4.3 Degradation of γ-hexachlorocyclohexane by indirect photooxidation 4.3.1 Evaluation of Raman spectra 4.3.2 Kinetics analysis 4.3.3 Characterization of lindane degradation products by NMR and mass spectrometry 4\. 4. Theoretical model for calculations 4.4.1 Model calculations and sample characterization with Raman and infrared (IR) spectroscopy 4.4.2 Terbuthylazine (TBA): theoretical and experimental Raman analysis 4.4.2.1 Characterization of the results of TBA photolysis by infrared spectroscopy (IR) 4.4.3 Simazine (6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine) 4.4.4 Lindane (gamma- hexachlorocyclohexane, (γ-HCH)) 4.5 Environmental Aspects and the possibility of the application of Raman microscopy 4.6 Summary 5\. Conclusion List of figures Lists of schemes List of tables References APPENDIX