Investigating Non-Targeted Screening and Accurate Quantitation of Trace Surface Water Contaminants Using High-Resolution Mass Spectrometry
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Western University Scholarship@Western Electronic Thesis and Dissertation Repository 8-8-2018 3:00 PM Investigating non-targeted screening and accurate quantitation of trace surface water contaminants using high-resolution mass spectrometry Lucas M. Morrison The University of Western Ontario Supervisor Sumarah, Mark W. The University of Western Ontario Co-Supervisor Yeung, Ken K-C. The University of Western Ontario Graduate Program in Chemistry A thesis submitted in partial fulfillment of the equirr ements for the degree in Master of Science © Lucas M. Morrison 2018 Follow this and additional works at: https://ir.lib.uwo.ca/etd Part of the Analytical Chemistry Commons, and the Environmental Chemistry Commons Recommended Citation Morrison, Lucas M., "Investigating non-targeted screening and accurate quantitation of trace surface water contaminants using high-resolution mass spectrometry" (2018). Electronic Thesis and Dissertation Repository. 5612. https://ir.lib.uwo.ca/etd/5612 This Dissertation/Thesis is brought to you for free and open access by Scholarship@Western. It has been accepted for inclusion in Electronic Thesis and Dissertation Repository by an authorized administrator of Scholarship@Western. For more information, please contact [email protected]. Abstract The human impact on surface water is a growing concern and the chemical surveying of contaminants including pharmaceuticals and pesticides is currently lacking. Neonicotinoids in particular, are among the most widely used insecticides that have prompted environmental concern and require monitoring. Chemical contaminants in environmental water samples are commonly analyzed by targeted tandem mass spectrometry. However, this requires a prior knowledge of the contaminants in the area of interest. Here, surface water samples were screened by utilizing optimized data-independent acquisition (DIA) methods and the spectra were databased for future retrospective analysis. This circumvents the requirement for target analytes prior to analysis and allows for improved method development. Methods were produced for the improved screening of contaminants using DIA, for the quantitation of targeted compounds, and to allow for the high-throughput analysis of neonicotinoids. Quantitation was completed for the detected compounds at various surface water sites and wastewater treatment plants. Keywords Analytical Chemistry, Environmental Analysis, Solid Phase Extraction, Lyophilisation, Mass Spectrometry, Non-Targeted Screening, Data-Independent Acquisition, Trace Residue Quantitation. ii Co-Authorship Statement Chapter 2: Morrison LM, Lapen D, Topp E, Manoli K, Renaud J, Yeung K and Sumarah M This chapter was written in its entirety by LMM. LMM and KM carried out all experiments with the help of apprentices. LMM designed and carried out all sample extractions and analyses. KM completed oxidation reactions on samples in section 2.6. Samples for section 2.4, 2.7 and 2.8 were provided by DL. Samples for section 2.5 and 2.6 were provided by ET and KM respectively. JR, KY, and MS provided expert advice on experimental design and analysis. Chapter 3: Morrison LM, Renaud J, Lapen D, Sabourin L, Yeung K and Sumarah M This paper was written by LMM. All experiments were executed by LMM. Samples were provided by DL. LMM and JR developed extraction protocol. LMM produced and carried out all LCMS analyses. LS, KY, and MS provided expert advice and authors read and provided edits for approval of the final manuscript. iii Acknowledgments I am very grateful to my supervisor Dr. Mark Sumarah for taking a chance on a student from Sudbury who knew nothing about mass spectrometry. His passion to produce important results and push the limits of the field has driven me to become a better scientist. Mark and my co-supervisor Dr. Ken Yeung have provided brilliant advice about both research goals and demonstrating ideas. I am very lucky to have had two admirable supervisors. Without the mentorship of Dr. Justin Renaud I am sure that my understanding of mass spectrometry would be abysmal in comparison. He makes tedious analysis sound like a treat that should be relished. He has a great eye for important findings and I am glad he was there to point out all those that I had missed. I appreciate the constant discussion and comradery provided by my fellow students in the Sumarah Lab Jacob Walsh, Natasha DesRochers and a big thanks to interns Derek Holzscherer, Ben Top and Yousef Risha, for technical assistance with the overwhelming number of water samples that are still being processed to this day. I would like to thank Lyne Sabourin for helping me get out of the lab and experience some field work. Megan Kelman and Stephanie Collins get full recognition for showing me the way to thesis writing and other grad school woes. I would like to thank our AAFC collaborators in London and Ottawa, in particular David Lapen for project design and Graham Wilkes for sample collection from the South Nation Conservation area. Dr. Edward Topp has helped me critically with key insights that only someone with his experience could provide. Finally I would like to thank my friends and family for their constant support and belief in me along this journey. iv Table of Contents Abstract ............................................................................................................................... ii Co-Authorship Statement................................................................................................... iii Acknowledgments.............................................................................................................. iv Table of Contents ................................................................................................................ v List of Tables ..................................................................................................................... ix List of Figures .................................................................................................................... xi List of Appendices ........................................................................................................... xiv List of Abbreviations ........................................................................................................ xv Chapter 1 ............................................................................................................................. 1 1 Introduction .................................................................................................................... 1 1.1 Environmental Contamination ................................................................................ 2 1.1.1 Pesticides..................................................................................................... 3 1.1.2 Pharmaceuticals .......................................................................................... 4 1.1.3 Artificial Sweeteners ................................................................................... 6 1.1.4 Industrial Pollutants .................................................................................... 6 1.1.5 Wastewater Treatment Plants ..................................................................... 7 1.2 Sample Preparation ................................................................................................. 8 1.2.1 Solid Phase Extraction (SPE)...................................................................... 8 1.2.2 Lyophilisation ............................................................................................. 9 1.2.3 Chromatographic Separation .................................................................... 10 1.3 Analytical Instrumentation.................................................................................... 11 1.3.1 Electrospray Ionization ............................................................................. 12 1.3.2 Atmospheric Pressure Chemical Ionization .............................................. 14 v 1.3.3 Mass Spectrometry.................................................................................... 15 1.4 Rationale and Aim ................................................................................................ 23 Chapter 2 ........................................................................................................................... 24 2 Comprehensive Screening of Environmental Contaminants in Surface Waters by Non- Targeted LC-MS and Quantitation on a Q-Exactive Orbitrap ..................................... 24 2.1 Abstract ................................................................................................................. 25 2.2 Introduction ........................................................................................................... 26 2.3 Experimental methods .......................................................................................... 29 2.3.1 Solid Phase Extraction (SPE).................................................................... 30 2.3.2 Chromatography Conditions ..................................................................... 32 2.3.3 Mass Spectrometry Conditions ................................................................. 34 2.3.4 Detection ................................................................................................... 34 2.3.5 Chemicals .................................................................................................. 37 2.3.6 Standard spiking solutions .......................................................................