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Development of Slow Release Nano Composite Fertilizer Using DEVELOPMENT OF SLOW-RELEASE NANO-COMPOSITE FERTILIZER USING BIODEGRADABLE SUPERABSORBENT POLYMER By Benard Kiplangat Rop I80/50014/2015 Department of Chemistry, University of Nairobi A Thesis Submitted in Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Chemistry of the University of Nairobi November, 2019 1 DECLARATION I declare that this thesis is my original work and has not been submitted elsewhere for examination, award of degree or publication. Where other people’s work or my own has been used, this property has been acknowledged and referenced in accordance with the University of Nairobi’s requirements. Signature____________________ Date__________________________ Benard Kiplangat Rop I80/50014/2015 Department of Chemistry, School of Physical Sciences, University of Nairobi This thesis has been submitted for examination with our approval as research supervisors. 1. Dr. Damaris Mbui Signature________________ Date______________ Department of Chemistry, University of Nairobi 2. Dr. George N. Karuku Signature________________ Date______________ Department of Land Resources & Agricultural Technology, University of Nairobi 3. Dr. Njagi Njomo Signature________________ Date______________ Department of Chemistry, University of Nairobi 4. Dr. Immaculate Michira Signature________________ Date______________ Department of Chemistry, University of Nairobi i DEDICATION My wife Gladys for her constant love, support and encouragement throughout this journey; I couldn’t have done it without you. My sons, Brian, Ian and Allan ii ACKNOWLEDGMENT I would like to sincerely and gratefully thank my supervisors, Dr. Damaris Mbui, Dr. George N. Karuku, Dr. Njagi Njomo and Dr. Immaculate Michira, all from the University of Nairobi for their support, guidance, understanding and friendship during my studies. They gave me an opportunity to work independently with their guidance. They encouraged me to grow as a researcher and an independent thinker. I highly appreciate everything you taught me. I would also like to thank University of Nairobi laboratory staff, Mr. Evans Kimega and Ms Rose Mutungi from the Department of Chemistry for their technical assistance during the synthesis of the copolymer and formulation of nano-composite fertilizer, Mr. John M. Kimotho and Mr. Ferdinand Anyika from the Department of Land Resources & Agricultural Technology for assisting in laboratory incubation and greenhouse experiments, and Mr. Edwin Rono from Centre for Biotechnology and Bioinformatics for his assistance in microbial culture and biodegradation test. I thank Dr. Rachel F. Ajayi from the University of Western Cape, S. Africa, for transmission electron microscopic (TEM) analysis of the samples. I would like to thank DAAD for the scholarship award and National Research Fund (NRF) for funding this research. I couldn’t have done without them. Most importantly, thanks to the persons I owe everything I am today; my wife Gladys, my sister Beatrice, my uncles J. Mutai and M. Mutai, my aunties Nancy, Rachel, Mary, Grace, for their unlimited love, concern, support and strength all these years. None of this could have been possible without them. iii PUBLICATIONS 1. Kiplangat Rop, Damaris Mbui, Njagi Njomo, George N. Karuku, Immaculate Michira, Rachel F Ajayi (2019), Biodegradable water hyacinth cellulose-graft-poly(ammonium acrylate-co-acrylic acid) polymer hydrogel for potential agricultural application, Heliyon, 5(3): e01416. 2. Kiplangat Rop, George N. Karuku, Damaris Mbui, Immaculate Michira, Njagi Njomo (2018), Formulation of slow release NPK fertilizer (cellulose-graft- poly(acrylamide)/nano-hydroxyapatite/soluble fertilizer) composite and evaluating its N mineralization potential, Annals of Agricultural Sciences, 63: 163-172. 3. Kiplangat Rop, George N. Karuku, Damaris Mbui, Njagi Njomo, Immaculate Michira (2019), Evaluating the effects of formulated nano-NPK slow release fertilizer composite on the performance and yield of maize, kale and capsicum, Annals of Agricultural Sciences, 64: 9-19. Patent Application Patent application No. 3319, Filed June, 2019, Kenya Industrial Property Institute (KIPI) iv ABSTRACT This work aimed at developing a slow release nano-composite fertilizer (SRF) for improved nutrient use efficiency in soil using a biodegradable superabsorbent polymer. Partially neutralized acrylic acid was grafted onto cellulose isolated from water hyacinth by radical polymerization reaction. The reaction conditions were optimized through assessment of grafting parameters namely, grafting cross-linking percentage (GCP), percentage grafting cross-linking efficiency (%GCE) and water absorption tests. The copolymer was characterized by Fourier transform infra-red (FTIR) spectroscopy, X-ray diffraction (XRD), Transmission electron microscopy (TEM) and Energy dispersive X-ray (EDX) spectroscopy. Water absorbency of the copolymer hydrogel was assessed in saline solutions and in solutions of various pH values. Degradation of the copolymer was tested by soil burial test and microbial culture isolated from agricultural soil. The optimized product exhibited superabsorbent qualities in distilled water and the water absorbency was influenced by pH and by the presence, nature and concentration of ions. The copolymer revealed the capacity to retain moisture in soil and degradation both in soil and microbial culture. A SRF was formulated by incorporating nano-hydroxyapatite (nano-HA), urea, (NH4)2HPO4 and K2SO4 into the cellulose grafted copolymer, and the release of nutrients was assessed using laboratory incubation experiment. Significantly higher (p≤0.05) content of mineral nitrogen (mineral-N) was observed in the first 4 weeks in conventional fertilizer (CF) compared to SRF treatments and the control. Mineral-N content in SRF treatments increased considerably between the 8th and 12th week, and declined in the 16th week. The values of potentially mineralizable N estimated using single first-order kinetics model related well to the observed cumulative mineral-N at 16th week. Significantly higher P content was observed in CF compared to SRF treatment in the 4th week, whereas in the 8th week, some SRFs released significantly higher content than CF. The data revealed reduced chances of leaching losses and toxic effect to the plant roots, as well as synchronized nutrient release to cater for the requirement by crops. Effect of the formulated SRF on the performance and yield of maize, kale and capsicum was evaluated in a greenhouse experiment. SRF recorded higher dry matter and yields relative to CF with similar application rates, though statistically insignificant. The agronomic optimal application rates of SRF determined by quadratic function were higher than that of CF. SRF enhance growth and yields of crops just like CF and could potentially have greater benefits such as improving soil health and resilience. Therefore, a slow release nano- composite fertilizer has been fabricated and investigated under laboratory and greenhouse (controlled) conditions. It is recommended that the formulated SRF be tested under field conditions. v TABLE OF CONTENTS DECLARATION ........................................................................................................................ i DEDICATION ........................................................................................................................... ii ACKNOWLEDGMENT ........................................................................................................... iii PUBLICATIONS ...................................................................................................................... iv ABSTRACT ...............................................................................................................................v LIST OF TABLES ......................................................................................................................x LIST OF FIGURES ................................................................................................................. xii LIST OF SCHEMES ................................................................................................................xiv LIST OF ABBREVIATIONS, SYMBOLS AND ACRONYMS ............................................... xv APPENDICES ...................................................................................................................... xviii CHAPTER ONE .........................................................................................................................1 1.0 INTRODUCTION .................................................................................................................1 1.1 Background information ........................................................................................................1 1.2 Statement of the problem .......................................................................................................5 1.3 Objectives .............................................................................................................................6 1.3.1 General objective ....................................................................................................6 1.3.2 Specific objectives ..................................................................................................6 1.4 Justification of the study ........................................................................................................6 1.5 Hypotheses ............................................................................................................................8
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