Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1972 Oxidation-Reduction Reactions of Sulfate and Sulfide in loF oded and Nonflooded Soil. Robert Mclure Engler Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Engler, Robert Mclure, "Oxidation-Reduction Reactions of Sulfate and Sulfide in Flooded and Nonflooded Soil." (1972). LSU Historical Dissertations and Theses. 2280. https://digitalcommons.lsu.edu/gradschool_disstheses/2280 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. 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University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 48106 A Xerox Education Company 73-2953 ENGLER, Robert McLure, 19^1- OXIDATION-REDUCTION REACTIONS OF SUIFATE AND SULFIDE IN FLOODED AND NONFLOODED SOIL. The Louisiana State University and Agricultural and Mechanical College, Ph.D., 1972 Agronomy University Microfilms, A XEROX Company, Ann Arbor, Michigan OXIDATION-REDUCTION REACTIONS OF SULFATE AND SULFIDE IN FLOODED AND NONFLOODED SOIL A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Agronomy by Robert McLure Engler B.S., Louisiana State University, 1967 M.S., Louisiana State University, 1969 August, 1972 PLEASE NOTE: Some pages may have indistinct print. Filmed as received. University Microfilms, A Xerox Education Company ACKNOWLEDGEMENT The writer wishes to express his sincere apprecia­ tion to Dr. W. H. Patrick, Jr., Professor of Agronomy, Louisiana State University for his assistance and gui­ dance during the course of this investigation. The author is indebted to his associates for their assistance and suggestions throughout this study and to Dr. W. H. Willis, Head of the Agronomy Department, who was instrumental in making this study possible. This research was supported in part by National Science Foundation Grant GB-8653 (General Ecology Sec­ tion) : due acknowledgement is made to this agency and to all other persons who in some way contributed to this investigation. The writer wishes to express his deep gratitude to his wife Pat, whose patience, encouragement and ability as a typist has been an inspiration and made this work possible. TABLE OF CONTENTS Page ACKNOWLEDGEMENT ...................................... ii LIST OF TABL E S ...................................... v LIST OF FIGURES ........................................ vi ABSTRACT ............................................ x INTRODUCTION ........................................ 1 REVIEW OF LITERATURE ............................... 4 A. Sulfide Accumulation in Submerged Soils . 4 1. Biochemistry of Soil Su l f i d e ......... 6 a. Sulfate-Reducing Micro­ organisms ...................... 6 b. Effect of Organic Matter .... 8 c. Effect of Oxidation-Reduction Potential ...................... 9 d. Effect of p H .......................11 2. Sulfide Toxicity ...................... 12 3. Source of Sulfide ......................... 14 4. Forms and Distribution of Soil S u l f i d e ..................................15 B. Effect of Oxidizing Compounds on Sulfide Accumulation in Submerged Soils ........... 17 1. Effect of O x y g e n ......................... 18 2. Effect of the Oxides of Nitrogen . 19 3. Effect of the Oxides of Manganese . 20 4. Effect of the Oxides of I r o n ............ 21 C. Effect of Sulfide on the Heavy Metals in Submerged Soils ............................. 23 1. Complexing of Heavy Metals by S u l f i d e ..................................25 a. Iron Sulfide .......................26 b. Manganese Sulfide ............... 27 c. Zinc and Copper Sulfide ............28 d. Mercury Sulfide .................... 29 D. Effect of the Rice Plant on Sulfide in Submerged Soils ............................. 30 MATERIALS AND METHODS ............................... 33 A. Soil Preparation ................................ 33 B. Obtaining Anaerobic Conditions .............. 34 iii TABLE OF CONTENTS (continued) Page C. Sulfide Determination ........................ 34 D. Measurement of Oxidation-Reduction P o t e n t i a l ...................................... 36 E. Sulfide Evolution from Rice Straw Radiolabelled with 35s ......................... 37 F. Sulfide Produced from Various Sulfur S o u r c e s ........................................ 40 G. Sulfide Production as Affected by Various Oxidants Added to a Soil Prior to Submerging ..................................41 H. Sulfide Production as Affected by Various Oxidants Added to a Reduced Submerged Soil After Maximum Sulfide F o r m a t i o n ...................................... 43 I. Heavy Metal Sulfide Reactions in Aerobic and Anaerobic S o i l s ........................... 44 J. Reactions of Mercury in Aerobic and Anaerobic Soils ............................. 48 K. Effect of the Rice Plant on Metal Sul­ fides in a Submerged S o i l .................... 52 RESULTS AND DISCUSSION ............................. 56 A. Sulfide Evolution from Rice Straw Labelled with 3 5 s ............................. 56 B. Sulfide Produced from Various Sulfur S o u r c e s ........................................ 58 C. Sulfide Production as Affected by Various Oxidants Added to a Soil Prior to Submerging ..................................62 D. Sulfide Production as Affected by Various Oxidants Added to a Reduced Submerged Soil After Maximum Sulfide F o r m a t i o n ...................................... 75 E. Heavy Metal Sulfide Reactions in Aerobic and Anaerobic Soils ............... 87 F. Reactions of Mercury in Aerobic and Anaerobic Soils ............................. 101 G. Effect of the Rice Plant on Metal Sulfides in a Submerged S o i l ................. Ill SUMMARY AND CONCLUSIONS ............................. 121 LITERATURE CITED ................................... 130 VITA .................................................. 137 iv LIST OF TABLES Table Page 1 The effects of 35g labelled Na~S, MnS, FeS, ZnS, CuS, and HgS placed in the lower rooting zone of a Crowley silt loam, on the yield of the aerial portion of the rice plant, uptake of 35s by the rice plant, and percent uptake of the added 35s by the rice plant ............................... 114 v LIST OF FIGURES Figure Page 1 A comparison of sulfide production from am organic and am inorganic sulfur source in a flooded Crowley silt loaun. Redox potential values are also shown . 57 2 Sulfide production from various inorganic sulfur sources added to a flooded Crow­ ley silt loaun.............................. 60 3 Sulfide produced from 100 and 200 ppm SO^-S added prior to flooding a Crowley silt loaun. Redox potential values are also s h o w n ................................ 63 4 Sulfide produced from 100 ppm S0 4 ~-S as affected by the addition of 300 ppm O2 , amd ferric oxide, equivalent to 300 ppm 0 2 / prior to flooding a Crowley silt loaun. Redox potential values are also s h o w n ....................................... 64 5 Sulfide produced from 100 amd 200 ppm S0 4 s-S as affected by the addition of potassium nitrate, equivalent to 300 amd 1 0 0 0 ppm O 2 , prior to flooding a Crowley silt loaun. Redox potential values are also shown ..................... 66 6 Sulfide produced from 100 and 200 ppm S0 4 s-S as affected by the addition of mamganese dioxide, equivalent