Order Number 8824578 Properties of synthetic goethites and their effect on sulfate adsorption Munoz, Miguel A., Ph.D. The Ohio State University, 1988 Copyright ©1988by Munoz, Miguel A. All rights reserved. UMI 300 N. Zeeb Rd. Ann Arbor, MI 48106 PLEASE NOTE: In all cases this material has been filmed in the best possible way from the available copy. Problems encountered with this document have been identified here with a check mark •/ . 1. Glossy photographs or pages. 2. Colored illustrations, paper or print • 3. Photographs with dark background _____ 4. Illustrations are poor copy ____ 5. Pages with black marks, not original copy ^ 6. Print shows through as there is text on both sides of page ______ 7. Indistinct, broken or small print on several pages _______ 8. Print exceeds margin requirements______ 9. Tightly bound copy with print lost in spine _______ 10. Computer printout pages with indistinct print ______ 11. Page(s)___________ lacking when material received, and not available from school or author. 12. Page(s) seem to be missing in numbering only as text follows. 13. Two pages numbered . Text follows. 14. Curling and wrinkled pages S 15. Dissertation contains pages with print at a slant, filmed as received 16. Other PROPERTIES OF SYNTHETIC GOETHITES AND THEIR EFFECT ON SULFATE ADSORPTION DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of the Ohio State University By Miguel A. Munoz, B.S., M.S. The Ohio State University 1988 Dissertation Committee: Approved by Dr. J .M . Bigham Dr. S.J. Traina ^ ' ~ ^ c / Adviser Dr. F.L. Himes Department of Agronomy D r . R .T . Tettenhors t Copyright by Miguel A. Munoz 1988 DEDICATION To all of you who build dreams and are strong enough to wake up and make those dreams a reality. To my Homeland, my Country, ray People. DEDICATORIA A todos aquellos forjadores de suenos que tienen la suficiente fortaleza para despertar y hacer esos suenos una realidad. A mi Patria, mi Pueblo, mi Gente. ACKNOWLEDGMENTS I express my most sincere appreciation to Dr. Jerry M. Bigham, Dr. Sam J. Traina and Dr. Trevor G. Arscott for their valuable help, guidance and insight throughout the research. I am also grateful to Dr. Frank L. Himes and Dr. Rodney T. Tettenhorst for their suggestions and comments as members of the reading committee. I am very grateful to the Department of Agronomy and the Agriculture Experiment Station of the University of Puerto Rico for their financial support while pursuing this degree. A special appreciation is extended to Dr. Clifford T. Johnston at the University of Florida for his valuable help with the FTIR study. I would also like to thanks Dr. William F. Jaynes who very kindly help me with the XRD analysis and the TEM study. I wish to specially acknowledge the love and support of my wife, Fuly. We have shared the good and the bad times and always managed to keep a smile at the end of the road. iii VITA April 14, 1956 ................. Born - Aguada, Puerto Rico 1978 ............................ B.S. in Agronomy University of Puerto Rico Mayaguez, Campus 1983 ............................ M.S. in Soil Fertility Thesis Topic: Phosphorus Absorption by Corn at Different Moisture Levels The Ohio State.University 1976-1981 ........................ Research Assistant Sugarcane Breeding Program, Agricultural Experimental Station University of Puerto Rico 1984-1986 ........................ Graduate Teaching Associate, Romance Languages Department The Ohio State University FIELDS OF STUDY Major field: Agronomy TABLE OF CONTENTS Page DEDICATION..................................... ii ACKNOWLEDGMENTS........................................ iii VITA.................................................... iv LIST OF TABLES......................................... ix LIST OF FIGURES........................................ xii INTRODUCTION.................................... 1 CHAPTER I. A REVIEW OF IRON OXIDES INSOILS ................ 7 1.1 Hematite (a-Fe203).............................. 10 1.2 Lepidocrocite (8-FeOOH). ..................... 11 1.3 Ferrihydrite (5Fe2Q3 . 9H20)..................... 13 1.4 Feroxyhite (6'-FeOOH)........................... 15 1.5 Maghemite (tf-Fe203)............................ 17 1.6 Magnetite (FesOO ............................... 19 1.7 Goethite (a-FeOOH).............................. 19 II. PROPERTIES AND SYNTHESIS OF GOETHITE........... 22 2.1 Structure of Goethite.......................... 22 2.2 Composition of Goethite........................ 26 2.3 Goethite Morphology............. 29 2.4 Thermal Properties of Goethite................. 37 2.5 Synthesis and Formation of Goethite............ 39 2.5.1 Synthesis of Goethites..................... 39 2.5.2 Factors Affecting the Formation of Goethite............................. 40 v 2.6 Materials and Methods.......................... 48 2.6.1 Sample Preparation....... 48 2.6.1.1 Al-substituted Goethites.......... 48 2.6.1.2 Hydrothermally Treated Goethites........................ 51 2.6.1.3 Nipe Soil Clay..................... 51 2.6.2 Characterization of the Synthetic Oxides and Nipe Soil Clay.............. 53 2.6.2.1 X-ray Powder Diffraction.......... 53 2.6.2.2 Calculation of Unit Cell Dimensions and Mean Crystallite Dimensions (MCD).... 54 2.6.2.3 Transmission Electron Microscopy....................... 57 2.6.2.4 Differential Scanning Calorimetry (DSC)............... 59 2.6.2.5 Surface Area....................... 59 2.6.2.6 Determination of Total Iron, Total Aluminum and Oxalate Soluble Iron..................... 59 2.6.2.7 Reductant-soluble Iron Content of Nipe Clay..................... 60 2.7 Results and Discussion......................... 61 2.7.1 Synthesis of Al-substituted Goethites.... 61 2.7.2 X-ray Diffraction Studies................. 64 2.7.2.1 Effect of A1 substitution on lattice spacing, unit cell dimensions and mean crystallite dimensions (MCD)................ 66 2.7.3 Surface Area of Al-goethites.............. 73 2.7.4 Transmission Electron Microscopy (TEM)... 76 2.7.5 Dehydroxylation Properties of Al- goethites................................ 80 2.7.6 Conclusions of the Synthesis and Characterization of Al-substituted Goethites................................ 84 2.7.7 Synthesis and Characterization of Hydrothermally-treated Goethites...... 85 vi 2.7.8 Conclusions of the Synthesis and Characterization of Hydrothermally- treated Goethites....................... 96 2.7.9 Characterization of Nipe Clay............ 96 III. INFRARED SPECTROSCOPY STUDY.................... 101 3.1 Infrared (IR) Characterization of Goethite: a Review...................................... 103 3.2 Infrared Spectroscopy Studies of Anion Adsorption.................................... 108 3.3 Infrared Spectroscopy of Sulfate and Sulfate Complexes............................ 110 3.4 Materials and Methods......... ............... 113 3.4.1 FTIR Characterization of the Adsorbents.. 114 3.4.2 FTIR Study of Sulfate Adsorption on Goethite................................. 116 3.5 Results and Discussion......................... 119 3.5.1 Characterization of the Adsorbents...... 119 3.5.2 FTIR Study of Sulfate Adsorption on Goethite................................. 134 3.5.3 Conclusions from the IR Study............ 156 IV. ADSORPTION ISOTHERMS............................ 157 4.1 Surface Charge of Oxides as Related to Sulfate Adsorption........................... 157 4.2 Adsorption Isotherms............................ 163 4.3 Materials and Methods.......................... 168 4.3.1 Preparation of Sulfate Adsorptio Isotherms................................ 168 4.4 Results and Discussion......................... 171 4.4.1 Al-substituted Goethites................. 171 4.4.2 Hydrothermally-treated Goethites and the Nipe Clay........................... 180 4.4.3 Sulfate Adsorption and OH Release....... 187 4.4.4 Conclusions............................... 193 vii V. SUMMARY.......................................... 196 BIBLIOGRAPHY............................................ 199 APPENDIX A. SULFATE ADSORPTION ISOTHERMS DATA............. 215 viii LIST OF TABLES Table No. Page 1.1 Some crystallographic data for the major Fe oxide minerals occurring in soils.................................... 9 2.1 Aluminum substitution in goethites........ 27 2.2 Chemical composition of soil goethites.... 30 2.3 Solution volumes for the preparation of the alurainum-goethite series.............. 50 2.4 Some physical and chemical properties of Al-substituted goethites............... 63 2.5 Unit cell dimensions and mean cystallite dimensions (MCD) of Al- substituted goethites............. 68 2.6 Average widths and lengths of particles from Al-substituted goethites as measured from electron micrographs and ratios of widths from XRD(MCDb) and TEM... 78 2.7 Oxalate soluble Fe content, surface area and mineralogy of hydrothermally-treated goethites................................... 86 2.8 Unit cell dimensions and mean crystallite dimensions (MCD) of hydrothermally-treated goethites................................... 89 ix Average widths and lengths of particles from hydrothermally-treated goethites as measured from electron micrographs and ratios of widths from XRD (MCDb) and TEM.. 92 Some chemical and physical properties of Nipe clay (< 2um).......................... 99 Infrared band positions of sulfate in selected complexes......................... 112 IR absorption frequencies of Al- goethites ................................ 124 IR absorption frequencies of hydrothermally-treated