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University Microfilms International A Bell & Howell Information Company 300 North Zeeb Road, Ann Arbor, Ml 48106-1346 USA 313/761-4700 800/521-0600 Order Number 9002006 The chemistry and mineralogy of phosphorus in excessively fertilized soils Pierzynski, Gary Michael, Ph.D. The Ohio State University, 1989 UMI 300 N. Zeeb Rd. Ann Arbor, MI 48106 THE CHEMISTRY AND MINERALOGY OF PHOSPHORUS IN EXCESSIVELY FERTILIZED SOILS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of the Ohio State University By Gary Michael Pierzynski, B.S., M.S * * * * * The Ohio State University 1989 Dissertation Committee: Approved By Dr. Terry J. Logan Dr. Samuel J. Traina Dr. Neil E. Smeck Adviser Department of Agronomy Dr. Gunter Faure ACKNOWLEDGEMENTS I wish to acknowledge, first and foremost, the love and support of my wife, Joy. This dissertation represents one of the few things that I will be leaving the Ohio State University with that I had originally planned on. The years have been filled with changes and adjustments and without the love and support of Joy, the completion of this dissertation would not have been possible. I am also deeply indebted to the members of my dissertation committee. My adviser, Dr. Terry Logan, has been extremely supportive and understanding of my professional and personal life. The remaining members of the committee, Drs. Traina, Smeck, Bigham, and Faure have also unselfishly provided suggestions and countless hours of discussions. The committee as a whole created an environment in which the only limitations before me were my own. I could not have asked for more. The financial assistance of the Tennessee Valley Authority, The Procter and Gamble Co., and the Department of Agronomy is also gratefully acknowledged. ii Finally, I would like to acknowledge the friendship vand assistance of the technicians, secretaries, and fellow graduate students within the Department of Agronomy who have made my time here much more enjoyable. VITA September 4, 1959 .......... Born - Detroit, Michigan 1982......................... B.S., Michigan State University, East Lansing 1985......................... M.S., Michigan State University, East Lansing 1985-1989 ................... Graduate Research Associate, The Department of Agronomy, The Ohio State University, Columbus PUBLICATIONS Pierzynski, G.M., S.R. Crouch, and L.W. Jacobs. 1986. Use of direct-current plasma spectrophotometry for the determination of molybdenum in plant tissue digests and soil extracts. Commun. Soil Sci. Plant Anal. 17: 419- 428. Pierzynski, G.M., and L.W. Jacobs. 1986. Molybdenum accumulation by corn and soybeans from a molybdenum- rich sewage sludge. J. Environ. Qual. 15: 394-398. Pierzynski, G.M., and L.W. Jacobs. 1986. Extractability and plant availability of molybdenum from inorganic and sewage sludge sources. J. Environ. Qual. 15: 323-326. Pierzynski, G.M., T.J. Logan, J.M. Bigham, and S.J. Traina. 1988. Phosphorus chemistry in excessively fertilized Midwestern soils: Mineralogy. Agronomy Abstracts p. 203. Pierzynski, G.M., T.J. Logan, and S.J. Traina. 1988. Phosphorus chemistry in excessively fertilized Midwestern soils: Solubility equilibria. Agronomy Abstracts p. 201. FIELDS OF STUDY Major Field: Soil and Environmental Chemistry Studies in Phosphorus Soil Chemistry. Professor Terry J. Logan v TABLE OF CONTENTS Page ACKNOWLEDGEMENTS .................................. ii VITA .............................................. iv LIST OF TABLES .................................... viii LIST OF FIGURES................................. xi LIST OF PLATES ................................ xiv CHAPTER I. INTRODUCTION .............................. 1 1.1 Introduction ......................... 1 II. LITERATURE REVIEW....................... 5 2.1 Forms of P in the Soil and the Associated Nomenclature............ 5 2.2 Phosphate Solubility Equilibria. .. 8 2.2.1 High pH Soils................ 11 2.2.2 Low pH S o i l s ................ 14 2.3 Direct Methodologies for Studying P Solids in Soils.................. 15 2.4 Assessing P Availability in Excessively Fertilized Soils ........ 19 2.4.1 Availability Indices .......... 19 2.4.2 Excessively Fertilized Soils . 22 2.4.3 Potential Environmental Activity of Soil Applied P . 24 2.5 Objectives and Hypothesis.......... 27 vi TABLE OF CONTENTS (continued) Page III. PHOSPHATE CHEMISTRY IN EXCESSIVELY FERTILIZED MIDWESTERN SOILS: MINERALOGY. 29 3.1 Introduction......................... 29 3.2 Materials and Methods................. 31 3.3 Results and Discussion............... 38 3.3.1 Sample Chemical and Mineral- ogical Characterization........ 3.3.2 Total P in Particle Size and Density Separates............... 38 3.3.3 Electron Microscopy............ 41 3.3.4 X-ray Diffraction and Infrared Spectroscopy ................... 74 3.4 Conclusions......................... 77 IV. PHOSPHATE SOLUBILITY EQUILIBRIA IN EXCESSIVELY FERTILIZED MIDWESTERN SOILS. 80 4.1 Introduction......................... 80 4.2 Materials and Methods................. 83 4.3 Results and Discussion............... 85 4.3.1 Influence of Time on Selected Solution Parameters............ 85 4.3.2 Calcium Phosphates ............. 93 4.3.3 Aluminum Phosphates............ 103 4.3.4 Iron and Manganese Phosphates. 108 4.4 Conclusions........................... 110 V. UTILIZATION OF AN ANION EXCHANGE RESIN EXTRACTION TO ASSESS RESIDUAL AVAILABLE PHOSPHORUS................................ 113 5.1 Introduction......................... 113 5.2 Materials and Methods................. 116 5.3 Results and Discussion............... 118 5.4 Conclusions........................... 134 VI. THE CHEMISTRY AND MINERALOGY OF PHOSPHORUS IN EXCESSIVELY FERTILIZED SOILS: SUMMARY AND CONCLUSIONS........................... 136 6.1 Summary................................ 136 6.2 Conclusions........................... 139 REFERENCES........................................ 142 APPENDIX .......................................... 150 vii LIST OF TABLES Table Page 1. Soil sample characteristics................. 33 2. Total P in particle size fractions........ 40 3. Total P in density separates of the clay fractions.................................... 42 4. PPP values for all s o i l s ...................... 45 5. Phosphorus elemental associations..............57 6. Percent of P-rich particles with Al/Si> 2.0. 63 7. Percent of P-rich particles categorized as Al-X with (Al-P)/Si> 2 . 0 ................... 64 8. Measured solution parameters for the Plainfield soils ........................... 86 9. Measured solution parameters for the McBride soils............................... 87 10. Measured solution parameters for the Blount, mine spoil, and Howard samples . 88 11. Values of log IAP and its standard deviation for variscite and A1(0H)2H2P04 for all samples at t= 130 d ............................ 106 12. Resin extractable P values over time at R / S = 2 0 .........................................119 13. Supernatant P concentrations over time at R / S = 2 0 .........................................119 14. Supernatant P concentrations and pH for the Plainfield soils ....................... 121 viii LIST OF TABLES (continued) Table Page 15. Supernatant P concentrations and pH for the Metea soils........................... 121 16. Supernatant P concentrations and pH for the McBride soils......................... 122 17. Supernatant P concentrations and pH for the Blount soils ........................... 122 18. Supernatant P concentrations and pH for the Mine spoil and Howard samples........ 123 19. Resin extractable P as a percent of total P at each value of R / S ................... 133 20. Measured solution parameters for the Plain­ field samples at t= 42 - 124 d ........... 151 21. Measured solution parameters for the Metea samples at t= 42 - 124 d ................. 153 22. Measured solution parameters for the McBride samples at t= 42 - 124 d ................. 154 23. Measured solution