An-Najah National University Faculty of Graduate Studies Phytofiltration of Chromium (Cr) and Manganese (Mn) from polluted waters using Luffa Cylindrica By Ayat Tawfeeq Hassan Abu Sharbeh Supervisor Dr. Ibrahim Abu Shqair Co-Supervisor Dr. Maather Sawalha This Thesis is submitted in Partial Fulfillment of the Requirements for the Degree of Master of Environmental Science, Faculty of Graduate Studies, An-Najah National University, Nablus - Palestine. 2015 ii iii Dedication First of all, my greatest gratitude to Allah, To my family, specially my father and mother …. To my dear "Yousef"… To my country "Palestine "… To my teachers and partners … To all who help and encourage me in any way… iv Acknowledgments First of all, I am so grateful to Allah, who gives me the patience and power to finish my thesis. Special thanks and appreciation to my supervisors, Dr. Ibrahim Abu Shqair and Dr. Maather Sawalha for their supervision , efforts, suggestions and time they spent to correct and note my work until the last stage. Thanks also to technical staff at the department of chemistry at an- Najah National University, especially, Mr. Nafeth Dwekat for his help. My thanks and gratitude to my lovely family, sisters and brothers for their support and encouragement. Endless regard and thankfulness to all who benefited me in any way, to all dear friends … vi List of Contents No. Contents Page Dedication iii Acknowledgment iv Declaration3 v List of contents vi List of tables viii List of figures ix Abstract xi Chapter One: Introduction 1 1.1 Heavy metals 1 1.1.1 Manganese(II) 2 1.1.2 Chromium(III) 3 1.2 Traditional techniques 4 1.3 Phytofiltration 5 1.4 Luffa cylindrica 7 1.5 Objectives 10 1.6 Novelty 10 1.7 Hypothesis 10 1.8 Previous studies 11 Chapter Two: Methodology 18 2.1 Collection and treatment of biomass 18 2.2 Preparation of stock metal solutions 19 2.3 Preparation of stock hard cation solutions 19 2.4 Preparation of calibration curves 19 2.5 Metal quantification 20 2.6 Instrumentation 20 2.7 Studied parameters 21 2.7.1 Effect of contact time 21 2.7.2 Effect of initial metal ion concentration 21 2.7.3 Effect of temperature 21 2.7.4 pH profile experiment 22 2.7.5 Capacity studies 22 2.7.6 Effect of competing ions 23 2.8 Statistical analysis 23 Chapter Three: Results and discussion 25 3.1 Effect of contact time 25 3.2 Effect of temperature 26 3.3 Effect of initial metal ion concentration 27 3.4 Effect of pH 28 3.5 Binding capacity 31 vii 3.6 Effect of competing ions 32 3.7 Phytofiltration potential of Luffa Cylindrica 34 3.8 Application of adsorption isotherms 35 3.9 Rate order of the adsorption process 40 3.10 Gibbs free energy 44 Conclusion 46 Tables 47 References 54 صخلملا ب viii List of Tables NO. Table Page 1 Effect of contact time on the % removal of metals by 47 seeds. 2 Effect of contact time on the % removal of metals by 47 sponge. 3 Effect of temperature on the % removal of metals by seeds. 47 4 Effect of temperature on the % removal of metals by 48 sponge. 5 Effect of pH on the % removal of metals by seeds. 48 6 Effect of pH on the % removal of metals by sponge. 48 7 Effect of initial metal ion concentration on the % removal 49 by seeds. 8 Effect of initial metal ion concentration on the % removal 49 by sponge. 9 Effect of the presence of one metal on the percent removal 49 of the other by seeds. 10 Effect of hard ions on the percent removal of Cr3+ by 50 seeds. 11 Effect of hard ions on the percent removal of Mn2+ by 50 seeds. 12 Binding capacity for metal with seeds. 50 13 Application of Langmiur adsorption isotherm on % 51 removal of Cr3+ by seeds. 14 Application of Freundlich adsorption isotherm on the % 51 removal of M2+ by seeds. 15 Loss of various concentrations of Cr3+ by seeds with time. 51 16 Loss of various concentrations of Mn2+ by seeds with time. 51 17 Applying second order equation on the % removal of Cr3+ 52 by seeds. 18 Applying second order equation on the % removal of Mn2+ 52 by seeds. 19 Applying Khan and Singh equation on the % removal of 52 Cr3+ by seeds. 20 Applying Khan and Singh equation on the % removal of 53 Mn2+ by seeds. 21 A plot of q versus C for the % removal of Cr3+ by seeds. 53 e e 22 A plot of q versus C for % removal of Mn2+ by seeds. 53 e e ix List of Figures NO. Figure Page 1 L.Cylindrica; (a) young fruits, (b) matured fibers with 7 seeds. 2 Effect of contact time on the % removal of metals by 25 seeds. 3 Effect of contact time on the % removal of metals by 25 sponge. 4 Effect of temperature on the % removal of metals by 26 seeds. 5 Effect of temperature on the % removal of metals by 27 sponge. 6 Effect of initial metal ion concentration on the % 28 removal by seeds. 7 Effect of initial metal ion concentration on the % 28 removal by sponge. 8 Effect of pH on the % removal of metals by seeds. 29 9 Effect of pH on the % removal of metals by sponge. 29 10 Binding capacity of metals with seeds. 32 11 Effect of Mn2+ ions on the percent removal of Cr3+ ions 33 by seeds. 12 Effect of Cr3+ ions on the percent removal of Mn2+ ions 33 by seeds. 13 Effect of hard ions on the percent removal of Cr3+ ions 34 by seeds. 14 Effect of hard ions on the percent removal of Mn2+ ions 34 by seeds. 15 Applying Freundlich adsorption isotherm on the 38 adsorption of Mn (II) on seeds. 16 Applying Langmiur adsorption isotherm on the 38 adsorption of Mn (II) on seeds. 17 Applying Freundlich adsorption isotherm on the 39 adsorption of Cr (III) on seeds. 18 Applying Langmiur adsorption isotherm on the 39 adsorption of Cr (III) on seeds. 19 Loss of various concentrations of Cr (III) ions by seeds 40 with time. 20 Loss of various concentrations of Mn (II) ions by seeds 40 with time. 21 Applying a pseudo first order reaction on binding of Cr 41 (III) ions with seeds. x 22 Applying a pseudo first order reaction on binding of Mn 42 (II) ions with seeds. 23 Applying a pseudo second order reaction on binding of 42 Cr (III) ions with seeds. 24 Applying a pseudo second order reaction on binding of 43 Mn (II) ions with seeds. 25 Khan and Singh plots of ln (q / C ) versus q for Cr (III) 44 e e e and Mn (II) adsorption on seeds at 20 . 26 Adsorption of Cr (III) and Mn (II) ions on seeds at 20 44 using q versus C plot. e e .