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3 Phosphate Removal from Water Using Alginate/Carboxymethylcellulose/Aluminum Beads and Plaster of Paris Phosphorus Adsorption

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3 Phosphate Removal from Water Using Alginate/Carboxymethylcellulose/Aluminum Beads and Plaster of Paris Phosphorus Adsorption Potential Approach for the Adsorption of Phosphate from Agricultural Runoff using Plaster of Paris Powder and Hydrogel Beads by Srdjan Malicevic A Thesis presented to The University of Guelph In partial fulfilment of requirements for the degree of Master of Science in Engineering Guelph, Ontario, Canada © Srdjan Malicevic, May, 2020 ABSTRACT POTENTIAL APPROACH FOR THE ADSORPTION OF PHOSPHATE FROM AGRICULTURAL RUNOFF USING PLASTER OF PARIS POWDER AND HYDROGEL BEADS Srdjan Malicevic Advisor(s): University of Guelph, 2020 Dr. Erica Pensini Dr. Prasad Daggupati Phosphorus released in lakes due to agricultural runoff causes eutrophication, deteriorating water quality and ecosystem harm. Adsorbing and recovering phosphorus could potentially contribute to a circular economy and reduce eutrophication. A literature review of phosphorus adsorbents was conducted to isolate for ideal adsorbents after defining criteria for surface water adsorption. Two adsorbents were studied for the removal of phosphate from water: plaster of Paris powder and hydrogel beads produced using alginate, carboxymethylcellulose, and aluminum. The reaction kinetics, adsorption capacity, and ability to desorb were compared. In deionised water, hydrogel beads had a 3- maximum sorption capacity of 90.5 mg PO4 /g dry bead with an equilibration time of approximately 24 hours. In deionised water, plaster of Paris (POP) powder has a 3- maximum capacity of 1.52 mg PO4 /g with an equilibrium time of less than 10 minutes. Sorbents can potentially be reused following phosphate desorption, and desorbed phosphate may be reused as fertilizer. iii ACKNOWLEDGEMENTS I would like to thank Dr. Erica Pensini for her mentorship and guidance during my degree and research. I would also like to thank Dr. Prasad Daggupatti for his assistance and advice on field-scale applications. I am grateful for the support from my peers such as Kristine Lamont, Samantha Mehltretter, Stephen Vanderburgt, and many more. I would like to especially thank Klaudine Estepa for her unending support and help in setting up experimental methods. The research described in this paper was funded by the Ontario Ministry of Food, Agriculture and Rural Affairs (OMAFRA) through the OMAFRA UofG program awarded to Drs. Erica Pensini and Prasad Daguppati. This research was also supported through the Mitacs Globalink program, with funding awarded to Ana Paula Garcia Pacheco and Erica Pensini. The authors greatly appreciate the support offered throughout the project by Joanne Ryks and Ryan Smith at the University of Guelph. iv TABLE OF CONTENTS Abstract ............................................................................................................................ii Acknowledgements ......................................................................................................... iii Table of Contents ............................................................................................................iv List of Tables .................................................................................................................. vii List of Figures ................................................................................................................ viii List of Appendices ........................................................................................................... x 1 Introduction .............................................................................................................. 1 1.1 Thesis Structure ................................................................................................. 1 1.2 Research Context .............................................................................................. 1 1.2.1 Phosphorus Removal .................................................................................. 1 1.2.2 Review of Phosphorus Sources and Sinks .................................................. 3 1.3 Problem Statement and Objective ...................................................................... 6 2 Literature Review ..................................................................................................... 8 2.1 Phosphorus ........................................................................................................ 8 2.2 Existing Technology for Phosphorus Removal ................................................. 10 2.3 Adsorption Dynamics and Adsorbent Material Classifications ......................... 13 v 2.3.1 Polymeric Adsorbents: Hydrogels .............................................................. 16 2.3.2 Adsorption Isotherms and Reversibility ..................................................... 21 2.3.3 Design Constraints and Criteria for Adsorbents Intended for Surface Water 26 2.3.4 Literature Review on Phosphorus Adsorbents ........................................... 30 2.3.5 Selected Materials for Phosphorus Adsorption .......................................... 33 3 Phosphate Removal from Water Using Alginate/Carboxymethylcellulose/Aluminum Beads and Plaster of Paris Phosphorus Adsorption ...................................................... 34 3.1.1 Materials .................................................................................................... 34 3.1.2 ALG-CMC (ACMC) bead preparation ........................................................ 34 3.1.3 Shear Rheology Experiments .................................................................... 35 3.1.4 Analytical Methods for Phosphorus Detection ........................................... 36 3.1.5 Phosphate Sorption and Desorption Experiments ..................................... 36 3.1.6 Modeling Approach .................................................................................... 37 3.1.7 Statistical Assumptions for Non-linear Fitting of Isotherms ........................ 39 3.2 Results and Discussion .................................................................................... 40 3.2.1 Sorption of Phosphorus onto POP powder ................................................ 40 3.2.2 Desorption of Phosphorus from POP powder ............................................ 44 3.2.3 Sorption of Phosphorus onto ACMC beads ............................................... 45 vi 3.2.4 Effect of Competing ions on Sorption of Phosphorus onto ACMC beads .. 52 3.2.5 Desorption of Phosphorus from ACMC beads ........................................... 52 4 Conclusion ............................................................................................................. 54 4.1 Phosphorus Sorption ........................................................................................ 54 4.2 Future Work ..................................................................................................... 57 References .................................................................................................................... 59 Appendices ................................................................................................................... 76 vii LIST OF TABLES Table 1 Hydrogel compositions and definitions ............................................................. 16 Table 2 Adsorption mechanisms and related inter/intramolecular force ........................ 19 Table 3 Summary of reversibility constants and isotherm shapes ................................. 24 Table 4 Relationship between adsorbent criteria and comparison between chemisorption and physisorption ................................................................................... 29 Table 5 Literature review on adsorbent materials and performance ............................. 31 Table 6 Nonlinear isotherm parameters for sorption of phosphate onto POP powder at pH= 7. ........................................................................................................................... 42 Table 7 Isotherm parameters for sorption of phosphate onto POP powder at pH= 7. ... 42 Table 8 Sorption capacity of beads having different composition, at pH= 7. The initial 3- phosphate concentration in DI was 2 mg/L PO4 .......................................................... 46 Table 9 Nonlinear isotherm parameters for sorption of phosphate onto ACMC beads at pH = 7 ........................................................................................................................... 49 Table 10 Linear isotherm parameters for sorption of phosphate onto ACMC beads at pH = 7 ................................................................................................................................. 49 Table 11: Comparison of materials with constraints and criteria with all factors determined .................................................................................................................... 56 viii LIST OF FIGURES Figure 1 Google Earth satellite image of Lake Erie on October 9th 2011......................... 2 Figure 2 Conceptual diagram of holistic nutrient transport denoting “N” as nitrogen and “P” as phosphorus; font size indicates greater relative loss through each respective pathway ........................................................................................................................... 7 Figure 3 Generalized phosphorus cycle and concept behind a circular economy for phosphorus adsorption and desorption/recovery ............................................................ 8 Figure 4 Chemical structure of orthophosphate .............................................................. 9 Figure 5 pH-logC
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