DEVELOPMENT OF MICROEXTRACTION-BASED TECHNIQUES FOR QUANTIFICATION AND BEHAVIOR CHARACTERIZATION OF NANOPARTICLES IN AQUATIC ENVIRONMENTS SEYED MOHAMMAD MAJEDI NATIONAL UNIVERSITY OF SINGAPORE 2014 DEVELOPMENT OF MICROEXTRACTION-BASED TECHNIQUES FOR QUANTIFICATION AND BEHAVIOR CHARACTERIZATION OF NANOPARTICLES IN AQUATIC ENVIRONMENTS SEYED MOHAMMAD MAJEDI (M.Sc., AMIRKABIR UNIVERSITY OF TECHNOLOGY) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMISTRY NATIONAL UNIVERSITY OF SINGAPORE 2014 Thesis Declaration I hereby declare that the work reported in this thesis is my original work performed independently between 02/08/2010 and 01/06/2014 The current thesis has been entirely written by me, and has not been submitted previously for any degree in any university I have duly acknowledged all the sources of information which have been used in this thesis Some contents of the thesis have been published in: [1] S.M Majedi, B.C Kelly, H.K Lee, Combined effects of water temperature and chemistry on the environmental fate and behavior of nanosized zinc oxide, Science of The Total Environment 496 (2014) 585 [2] S.M Majedi, B.C Kelly, H.K Lee, Evaluation of a cloud point extraction approach for the preconcentration and quantification of trace CuO nanoparticles in environmental waters, Analytica Chimica Acta 814 (2014) 39 [3] S.M Majedi, B.C Kelly, H.K Lee, Role of combinatorial environmental factors in the behavior and fate of ZnO nanoparticles in aqueous systems: A multiparametric analysis, Journal of Hazardous Materials 264 (2014) 370 [4] S.M Majedi, B.C Kelly, H.K Lee, Toward a robust analytical method for separating trace levels of nano-materials in natural waters: Cloud point extraction of nano-copper(II) oxide, Environmental Science and Pollution Research 21 (2014) 11811 i [5] S.M Majedi, B.C Kelly, H.K Lee, Efficient hydrophobization and solvent microextraction for determination of trace nano-sized silver and titanium dioxide in natural waters, Analytica Chimica Acta 789 (2013) 47 [6] S.M Majedi, H.K Lee, B.C Kelly, Role of water temperature in the fate and transport of zinc oxide nanoparticles in aquatic environment, Journal of Physics: Conference Series 429 (2013) 012039, DOI: 10.1088/17426596/429/1/012039 [7] S.M Majedi, H.K Lee, B.C Kelly, Chemometric analytical approach for the cloud point extraction and inductively coupled plasma mass spectrometric determination of zinc oxide nanoparticles in water samples, Analytical Chemistry 84 (2012) 6546 Seyed Mohammad Majedi 12 August 2014 ii Acknowledgements My first and foremost gratitude goes to my supervisor, Professor Hian Kee Lee, for his continuous and unconditional support of my Ph.D study and research, invaluable suggestions, and for his patience and encouragement Under his guidance, I learnt how to research independently, and gained a number of valuable experiences My sincere thanks also go to my cosupervisor, Assistant Professor Barry C Kelly from Department of Civil and Environmental Engineering, for his kind support and precious comments throughout the research I also gratefully acknowledge the Agency for Science, Technology and Research (A STAR), Singapore, for the award of a research scholarship I would like to express my special thanks to my colleagues, Dr Hong Zhang, Dr Liang Guo, Dr Yufeng Zhang, Dr Dandan Ge, Mr Nyi Nyi Naing, Ms Ruyi Xu, Ms Zhenzhen Huang, Ms Claire Anne Taylor, Ms Maryam Lashgari, and Mr Sheng Tang, and all my friends, for their help and advice during my candidature I am also grateful to Mdm Lim Guek Choo, Frances and Ms Per Poh Geok (NUS Environmental Research Institute), Dr Liu Qiping (Depratment of Chemistry), Mr Sukiantor Bin Tokiman, Mr Mohamed Sidek Bin Ahmad, and Ms Chia Yuit Ching, Susan (Temasek Lab, Department of Civil and Environmental Engineering), Dr Jixuan Zhang and Ms Fengzhen Yang (Transmission Electron Microscopy Lab, Department of Material Science and iii Engineering), and many other staff and laboratory technologists at the Department of Chemistry, for their kind help and assistance Last but not the least, my deep appreciations go to my wife, Ms Samaneh Tavakolinia, for her endless love, support, and motivation, and my beloved little daughter, Arghavan, for making my student life joyful, and my dear parents, sisters, and the rest of my family, for their understanding, tolerance, and supporting me spiritually iv Table of Contents Thesis declaration i Acknowledgements iii Table of Contents v Summary x List of Tables xiii List of Figures xv List of Abbreviations xxi Chapter Introduction 1.1 Application and environmental implications of NPs 1.1.1 Application 1.1.2 Transformation in the environment 1.1.3 Toxicity 10 1.2 Identification and characterization of NPs .12 1.2.1 Microscopic techniques 13 1.2.2 Laser-based techniques 14 1.2.3 X-ray-based techniques 15 1.2.4 Surface charge and area analysis 16 1.3 Separation of NPs in aqueous media 17 1.3.1 Ultrafiltration and ultracentrifugation 17 1.3.2 Field-flow fractionation 19 v 1.3.3 Size exclusion chromatography .20 1.3.4 Electrophoresis 20 1.3.5 Two-phase separation 21 1.3.5.1 Liquid-liquid extraction .21 1.3.5.2 Cloud point extraction .23 1.4 Quantification of NPs 26 1.4.1 Elemental analysis 27 1.4.1.1 Inductively coupled plasma-mass spectrometry 27 1.4.1.2 Atomic absorption spectrometry 31 1.4.2 Electroanalytical methods 32 1.4.3 Spectroscopic methods 33 1.5 Objectives and scope of the study 35 Chapter Evaluation of a cloud point extraction for quantification of trace levels of copper(II) oxide nanoparticles in water 39 2.1 Introduction .39 2.2 Materials and methods .42 2.2.1 Chemicals 42 2.2.2 Cloud point extraction 44 2.2.3 Microwave digestion and elemental analysis 44 2.2.4 Dissolution and adsorption experiments 47 2.2.5 Preparation of coated CuO NPs .48 2.2.6 Characterization of CuO nanoparticles 49 2.3 Results and discussion .50 vi 2.3.1 Enrichment factor 50 2.3.2 Sample pH .53 2.3.3 Incubation conditions 57 2.3.4 Environmental interferences 61 2.3.5 Coating chemical 67 2.3.6 Sample analysis .73 2.3.7 Method validation 77 2.3.8 Genuine water sample analysis 79 2.4 Conclusion 81 Chapter Surface modification and solvent microextraction of trace silver and titanium dioxide nanoparticles in water 83 3.1 Introduction .83 3.2 Materials and methods .86 3.2.1 Chemicals 86 3.2.2 Surface functionalization, solvent extraction, and measurement of NPs 90 3.2.3 Characterization of Ag and TiO2 NPs 92 3.2.4 Selection of reagent type by experimental design 93 3.3 Results and discussion .96 3.3.1 Preliminary optimization .96 3.3.2 Effects of pertinent parameters 98 3.3.3 Effects of ultrasonication and centrifugation 103 3.3.4 Effects of NP size and concentration 105 vii 3.3.5 Effects of environmental factors 107 3.3.6 Characterization of Ag and TiO2 NPs 114 3.3.7 Method validation 125 3.3.8 Separation of Ag and TiO2 NPs in natural waters 126 3.4 Conclusion 131 Chapter Combined 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