INVESTIGATION OF A NOVEL APPROACH FOR ARSENIC REMOVAL FROM WATER USING MODIFIED RHYOLITE By VINOTH MANOHARAN Bachelor of Technology Perriyar University Tamilnadu, India 2002 Submitted to the Faculty of the Graduate College of the Oklahoma State University In partial fulfillment of the requirements for the degree of MASTER OF SCIENCE December, 2005 INVESTIGATION OF A NOVEL APPROACH FOR ARSENIC REMOVAL FROM WATER USING MODIFIED RHYOLITE Thesis Approved: Dr. John N. Veenstra Thesis Advisor Dr. Gregory G. Wilber Dr. Steve Cross Dr. A. Gordon Emslie Dean of the Graduate College ii ACKNOWLEDGEMENTS I extend my sincere gratitude and appreciation to many people who made this masters thesis possible. Special thanks are due to Dr. John N. Veenstra, my principal advisor for guidance and encouragement throughout my research work. I would like to express my sincere thanks to Dr. Steve Cross, a member of my advisory committee for his effort and support. I would like to extent my words of appreciation to Dr. Grergory G. Wilber for his help in troubleshooting of the lab equipments and his immediate presence whenever needed. Many thanks are due to the lab manager Mr. David Porter for helping me out in setting up experiments. I would also like to thank my friends Muralikrishnana Erat and Ann Mary Mathew for their constructive suggestions and the moral support they had offered. I am also thankful to Indumathi Appan, Arthi Krubanandh and Kirubhakaran Vyravan for their help at different stages of the research work. iii TABLE OF CONTENTS Chapter Page INTRODUCTION .......................................................................................................... 11 Overview......................................................................................................................... 1 Project Objective............................................................................................................. 2 ARSENIC BACKGROUND ............................................................................................ 3 Arsenic in Drinking Water.............................................................................................. 3 Speciation........................................................................................................................ 5 Toxicity and Health Effects ............................................................................................ 6 LITREATURE REVIEW ................................................................................................ 8 ARSENIC REMOVAL TECHNOLOGIES ................................................................... 8 Oxidation/Filtration..................................................................................................... 8 Co-precipitation .......................................................................................................... 9 Iron Coagulation ................................................................................................... 10 Alum Coagulation................................................................................................. 10 Lime softening ...................................................................................................... 10 Membrane Techniques.............................................................................................. 11 Reverse Osmosis .................................................................................................. 12 Nanofiltration ....................................................................................................... 12 Electrodialysis ...................................................................................................... 13 Sorption Techniques ............................................................................................... 133 Activated Alumina ............................................................................................... 15 iv Ion Exchange Resins............................................................................................. 16 Granular Ferric Hydroxide.................................................................................... 17 Iron Oxide Coated Sand ....................................................................................... 17 Auminum Loaded Shirasu Zeolite........................................................................ 18 Evaluation of Arsenic Removal Technologies ............................................................. 19 Overview of Emerging Technologies ......................................................................... 212 Synthetic Zeolites........................................................................................................ 222 Analytical Methods for Analysis of Arsenic in Drinking Water .................................. 26 Overview of Research Gaps.......................................................................................... 27 MATERIALS AND METHODS ................................................................................... 28 Sorption Media.............................................................................................................. 29 Glassware.................................................................................................................... 333 Reagents...................................................................................................................... 333 Instruments.................................................................................................................. 356 Methodology................................................................................................................. 38 RESULTS AND DISCUSSION ..................................................................................... 43 Experimental Quality Control....................................................................................... 43 Results and Discussion ................................................................................................. 46 Engineering Application ............................................................................................... 87 CONCLUSIONS ............................................................................................................. 89 REFERENCES.............................................................................................................. 901 APPENDICES................................................................................................................. 99 v LIST OF TABLES Table Page Table 1: Potential Short Term Health Effects …………………………………………….6 Table 2: Potential Long Term Health Effects …………………….………………………6 Table 3: Removal Efficiencies of Different Media ……………………………………...14 Table 4: Treatment Options and Maximum Achievable Percent Removal …………......20 Table 5: Approved Analytical Methods for Analysis of Arsenic in Drinking Water …..26 Table 6: Composition of Rhyolite and Shirasu ………………………………………….29 Table 7: Media and Treatment Steps Involved ………………………………………….39 Table 8: External Quality Control ……………………………………………………….46 Table 9: Reaction Order …………………………………………………………………53 Table 10: Freundlich Isotherm Constants – Zeolite and Non – zeolite …………………62 Table 11: Freundlich Isotherm Constant of Media ……………………………………...67 Table 12: Desorption and Readsorption with HCl ………………………………………70 Table 13: Desorption and Readsorption with HCl and NaOH ………………………….72 Table 14: Effect of Competing Ions ……………………………………………………..75 Table 15: TCLP Analysis ………………………………………………………………..79 Table 16: Comparison of Modified Rhyolite Vs Al-loaded Shirasu Zeolite ……………86 vi List of Figures Figure Page Figure 1: Groundwater Arsenic concentration Map of the United States ………………..4 Figure 2: Aqueous Arsenic Speciation ……………………………………………….......5 Figure 3: Basic Zeolite Framework …………………………………………..…………24 Figure 4: Exchange of Aluminum Ions ………………………………………………… 31 Figure 5: Formation of LTA Zeolite …………………………………………………….33 Figure 6: Making of Media …………………..…………………..…………………….. 40 Figure 7: Kinetics – Quarry Screenings with Chemical Treatment …..…………………48 Figure 8: Kinetics – Non-Zeolite made from Minus No. 50 Material, with Chemical Treatment ………………………………………..…………………………….49 Figure 9: Kinetics – Non-zeolite made from Minus No. 200 Material, with Chemical Treatment ………………………...……………………………………………51 Figure 10: Reaction Order ………………………………………………………………54 Figure 11: Investigation of Mechanism of Removal ……………………………………57 Figure 12: with Feldspar and Sandstone ………………………………………………...61 Figure 13: Isotherm – Zeolite vs Non-zeolite …………………………………………...63 Figure 14: Comparison with Other Media…… ……...………………………………….66 Figure 15: Capacity of the Medium ……………………………………………………..68 Figure 16: Effect of pH ………………………………………………………………….74 Figure 17: Arcenic(V) vs Arsenic(III) …………………………………………………..76 vii Figure 18: Effect of Aging ………………………………………………………………78 Figure 19: Column Study ………………………………………………………………..81 Figure 20: Operating Capacity of the Column …………………………………………..83 Figure 21: Operating Capacity for Batch Operation …………………………………….85 Figure 22: Arsenic Removal from Water with a Filtration Bed ………………………...87 Figure 23: Arsenic Removal from Water with a Contact Basin ………………………...88 viii CHAPTER I INTRODUCTION Overview In the process of human evolution, some of the issues confronting today’s society are safe guarding the natural environment and maintaining a good quality of life. However, a slight imbalance in any equilibrium in the environment is bound to manifest itself