Fate of Glucocorticoid Receptor Agonists During Water and Wastewater Treatment Processes
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Fate of Glucocorticoid Receptor Agonists During Water and Wastewater Treatment Processes Item Type text; Electronic Dissertation Authors Wu, Shimin Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 07/10/2021 19:56:47 Link to Item http://hdl.handle.net/10150/623167 FATE OF GLUCOCORTICOID RECEPTOR AGONISTS DURING WATER AND WASTEWATER TREATMENT PROCESSES by Shimin Wu __________________________ Copyright © Shimin Wu 2016 A Dissertation Submitted to the Faculty of the DEPARTMENT OF CHEMICAL AND ENVIRONMENTAL ENGINEERING In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY WITH A MAJOR IN ENVIRONMENTAL ENGINEERING In the Graduate College THE UNIVERSITY OF ARIZONA 2016 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE As members of the Dissertation Committee, we certify that we have read the dissertation prepared by Shimin Wu, titled Fate of Glucocorticoid Receptor Agonists During Water and Wastewater Treatment Processes and recommend that it be accepted as fulfilling the dissertation requirement for the Degree of Doctor of Philosophy. _______________________________________________________________________ Date: 11/29/2016 Dr. Shane A. Snyder _______________________________________________________________________ Date: 11/29/2016 Dr. Avelino E. Saez _______________________________________________________________________ Date: 11/29/2016 Dr. Robert G. Arnold _______________________________________________________________________ Date: 11/29/2016 Dr. James Farrell Final approval and acceptance of this dissertation is contingent upon the candidate’s submission of the final copies of the dissertation to the Graduate College. I hereby certify that I have read this dissertation prepared under my direction and recommend that it be accepted as fulfilling the dissertation requirement. ________________________________________________ Date: 11/29/2016 Dissertation Director: Dr. Shane A. Snyder ________________________________________________ Date: 11/29/2016 Dissertation Director: Dr. Avelino E. Saez 2 STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of the requirements for an advanced degree at the University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided that an accurate acknowledgement of the source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his or her judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED: Shimin Wu 3 TABLE OF CONTENTS List of Figures.................................................................................................................... 9 List of Tables ................................................................................................................... 12 List of Abbreviations ...................................................................................................... 15 Abstract............................................................................................................................ 17 1. Introduction............................................................................................................. 19 1.1. Glucocorticoid Receptor Agonists as An Emerging Concern .......................... 19 1.2. Use of Corticosteroids....................................................................................... 21 1.3. Toxicity of Corticosteroids ............................................................................... 26 1.4. Occurrence of Corticosteroids in the Aquatic Environment............................. 29 1.5. Removal of Corticosteroids in Water and Wastewater Treatment Processes... 30 1.6. Research Objectives.......................................................................................... 32 2. Trace Analysis of Glucocorticoid Receptor Agonists in Environmental Waters by Liquid Chromatography-Tandem Mass Spectrometry ......................................... 33 2.1. Introduction....................................................................................................... 33 2.2. Experimental Section........................................................................................ 36 2.2.1. Chemicals and Materials .......................................................................... 36 2.2.2. Sample Collection ..................................................................................... 37 2.2.3. Sample Extraction and Cleanup ............................................................... 37 2.2.4. Instruments and Operation Conditions..................................................... 38 2.2.5. Data Analysis............................................................................................ 39 2.3. Results and Discussion ..................................................................................... 40 4 2.3.1. Optimization for Multiple Reaction Monitoring Conditions in MS/MS.... 40 2.3.2. Optimization for Liquid Chromatography Conditions ............................. 44 2.3.3. Cleanup and Matrix Effects ...................................................................... 48 2.3.4. Method Validation .................................................................................... 49 2.4. Conclusions....................................................................................................... 53 3. Determination of Octanol-Water Partition Coefficients for Glucocorticoid Receptor Agonists ........................................................................................................... 54 3.1. Introduction....................................................................................................... 54 3.2. Experimental Section........................................................................................ 55 3.2.1. LogKow Calculation Programs.................................................................. 55 3.2.2. Experimental LogKow Dataset................................................................... 57 3.3. Results and Discussion ..................................................................................... 57 3.3.1. Performance of Different Computational Programs ................................ 57 3.3.2. Prediciton of LogKow for A Wide Range of Corticosteroids..................... 58 3.3.3. Comparison of LogKow for Different Classes of Steroid Hormones......... 65 3.4. Conclusions....................................................................................................... 66 4. Occurrence of Glucocorticoid Receptor Agonists in Surface Water and Groundwater ................................................................................................................... 67 4.1. Introduction....................................................................................................... 67 4.2. Experimental Section........................................................................................ 68 4.2.1. Chemicals and Materials .......................................................................... 68 4.2.2. Sample Collection ..................................................................................... 68 4.2.3. Sample Preparation and LC-MS/MS Analysis.......................................... 70 5 4.3. Results and Discussion ..................................................................................... 70 4.3.1. GR Agonists in the Lower Santa Cruz River............................................. 70 4.3.2. GR Activity in the Lower Santa Cruz River .............................................. 72 4.3.3. GR Agonists in Groundwater Along the Lower Santa Cruz River............ 74 4.4. Conclusions....................................................................................................... 75 5. Occurrence and Fate of Glucocorticoid Receptor Agonists in Wastewater Treatment Plants (WWTP)............................................................................................ 76 5.1. Introduction....................................................................................................... 76 5.2. Experimental Section........................................................................................ 77 5.2.1. Chemicals and Materials .......................................................................... 77 5.2.2. Sample Collection ..................................................................................... 77 5.2.3. Enzymatic Hydrolysis of Conjugated Corticosteroids.............................. 78 5.2.4. Sample Preparation and LC-MS/MS Analysis.......................................... 79 5.3. Results and Discussion ..................................................................................... 79 5.3.1. Occurrence of Corticosteroids in WWTP ................................................. 79 5.3.2. Removal of Corticosteroids in WWTP .....................................................