HYDROGEOCHEMISTRY AND SOURCES OF CHLORIDE AND SULFATE IN THE VERDIGRIS RIVER BASIN IN OKLAHOMA By CHARLES DANA RACE ) ( Bachelor of Arts University of Maine Orono, Maine 1981 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, 1985 HYDROGEOCHEMISTRY AND SOURCES OF CHLORIDE AND SULFATE IN THE VERDIGRIS RIVER BASIN IN OKLAHOMA Thesis Approved: D an of the Graduate College ii ACKNOWLEDGEMENTS I am greatful to my advisor, Professor Arthur W. Hounslow for his ideas and suggestions that guided me through the development of this study. Dr. Hounslow's limitless knowledge of hydrogeochemistry conveyed during discussions and in his courses have contributed immensely to this study. I am also indebted to Professor Wayne A. Pettyjohn for his suggestions which also contributed significantly to this thesis. Much knowledge ~as gained during discussions and his courses in hydrogeology. Professor R. Nowell Donovan offered suggestions on several occasions that aided the progress of this study. I am also greatful to Professors Donovan, Hounslow and Pettyjohn for their comments which led to the revision of the manuscript. Kelley, my wife, was also supportive and in many ways through her willpower and understanding helped me to achieve this goal. She also assisted me with the drafting and the format of the thesis. My thoughtful parents, Clarence A. and Pauline R. Race always provided moral support and helped us in many ways. iii Mr. Emmett Lorey and the late Helen Lorey provided an escape for us in St. Joseph, Missouri on several occasions. Many individuals, too numerous to mention, assisted in this study by providing background information. Agencies that cooperated in this effort were the U.S. Geological Survey, Oklahoma Geological Survey, U.S. Environmental Protection Agency, Oklahoma Water Resources Board, Oklahoma Conservation Commission, Oklahoma Department of Mines, Oklahoma State Department of Health Oklahoma Corporation Commission, and Bureau of Indian Affairs in Pawhuska, Oklahoma. iv TABLE OF CONTENTS Chapter Page I. INTRODUCTION . .. .. .. .. .. .. .. 1 Statement of Problem 1 Study Area ••••••••••••••• . 1 Objectives and Scope 3 Methodology •••••••••• 5 II. GEOLOGY . .. .. .. .. .. .. .. 7 Introduction •••.•••• • •••• 7 Previous Studies ••••• 7 Hominy Creek Basin •••••• • •••• 9 Alluvium and Terrace Deposits ••• 9 Vanoss Group •••••• • •••••. 9 Ada Group ••••• . ••••• 9 Vamoosa Formation ••••• • •••• 11 Tallant and Barnsdall Formations 11 Wann Fm, lola Ls, Chanute Fm 11 Nellie Bly and Hogshooter Fm 12 Coffeyville and Checkerboard Fm 12 Oologah Reservoir Area ••••••••••••••• 12 Alluvium and Terrace Deposits 12 Coffeyville, Checkerboard, Seminole 12 Lenapah and Nowata Formations 14 Oologah and Labette Formations. 14 Fort Scott Limestone •••••••• 14 Senora and Boggy Formations 15 Occurrence of Coal 15 Dawson Coal 15 Iron Post Coal ••••• .. 17 Croweburg Coal 17 Mineral Coal 17 Weir-Pittsburg Coal 17 III. HYDROGEOLOGY . .. .. .. .. .. .. 19 Previous Studies ••••••••••••••••••• 20 Hydrologic Cycle ••••••••••••••••••• 21 Alluvium and Terrace Aquifers 23 Vamoosa-Ada Aquifer .••••• 23 Pennsylvanian Rocks 24 v Chapter Page IV. HYDROGEOCHEMISTRY . .. 27 Introduction ••••••.•••••• 27 Geochemistry of Sulfur 33 Geochemistry of Chloride 36 Chemical Equilibrium Model 38 Chemical Analyses 38 Mineral Equilibria 40 Comparis~n of Mineral Equilibria 42 v. ACTIVITIES OF MAN . 44 Introduction •••••••• 44 Oil Field Activities 44 Introduction ••••• 44 Source of Information 45 Sulfur Content of Crude Oil 46 Oil and Gas Fields ••••••••• 46 Hominy Creek and Delaware·Creek Basins 46 Production Zones •••••• 46 Oil Field Brines 48 Oologah Reservoir Area 49 Panther Creek Basin 49 Spencer Creek Basin 49 Sources of Pollution •••••• so Contaminants Associated with Brines so Detection of Contaminants 51 Coal Field Activities ••••••• 52 Sources of Information 52 Oologah Reservoir Area 53 Introduction 53 Fourmile Creek 54 Lightning Creek 54 Panther Creek Basin 56 Plume Creek Basin 56 Spencer Creek Basin 56 Blue Creek Basin 59 Dog Creek Basin •••••••••••• 59 Effects and Detection of Contamination 62 VI. VERDIGRIS RIVER BASIN AND HOMINY CREEK BASIN 65 Verdigris River Basin 65 Introduction ••••• 65 Rainfall- ............. 65 Chemistry of Rainfall 65 Rainfall . ..... 66 Probability Graphs 66 Verdigris River Basin 68 Sources of Chloride 68 vi Chapter Page Sources of Sulfate 73 Ho.miny Creek Basin ...................... 75 Sources of Chloride ................ 75 Sources of Sulfate ...•.........•...• 75 Chloride and Sulfate •••••••••••••••• 75 Hominy Creek Basin ..••.••....•...••...... 76 Introduction •.••..•••••..••••..••.•. 76 Rainfall at Hominy •••••••••••••••••• 76 Control Stations •••••••••••••••••••• 76 Chloride Probability Graphs ••••••••• 78 Sources of Chloride •••••••••••••••.• 78 Sulfate Probability Graphs •••••••••• 83 Sources of Sulfate ••••••.•••••••••.• 83 Delaware Creek Basin ••••••••••••••••••••• 86 Ground Water in Hominy Creek Basin ••••••. 88 Chloride Probability Graph •••••••••• 88 Sulfate Probability Graph •••••••••.• 88 .Hominy Creek Basin Stream Survey ••••••••• 90 Probability Graph ••••••••••••••••••• 90 Sources of Chloride ••••••••••••••••• 90 VII. OOLOGAH RESERVOIR AREA AND DOG CREEK BASIN •.•• 96 Rainfall . 96 Control Stations •••••••••••••••••••• 96 Chloride Probability Graphs •••••••••••••• 96 Oologah Reservoir Area ••••••••••••••••••• 99 Sources of Chloride ••••••••••••••••• 99 Dog Creek Basin .......................... 103 Stream Observations ••••••••••••••••• 103 Sources of Chloride ••••••••••••••••• 103 Possible Sources of Chloride Contamination 105 Sulfate Probability Graphs ••••••••••••••• 106 Dog Creek Basin ..•....................... 106 Sources of Sulfate •••••••••.••.••••• 106 Oologah Reservoir Area ••••••••••••••••••• 109 Sources of Sulfate •••••••••••••••••• 109 Ground Water ...•......•..•.....••...•.••. 116 Chloride Probability Graphs ••.•••••• 116 Sources of Chloride ••••••••••••••••• 119 Sulfate Probability Graph ••••••••••• 122 Comparison of Probability Graphs •••••.••. 124 VIII. SUMMARY AND CONCLUSIONS •••••••••.•••••.••••••• 128 Summary ...•...•.•............•........... 128 Hydrologic Cycle .••••••••••••••••••• 129 Alluvial and Terrace Aquifers .•••••• 129 Vamoosa-Ada Aquifer •••••••••••••.••• 130 Pennsylvanian Rocks •••.••••••••••.•• 131 vii Chapter Page Conclusions ............................. 132 Verdigris River & Hominy Creek Basins 132 Hominy Creek & Delaware Creek Basins 133 Oologah Reservoir & Dog Creek Basin • 137 REFERENCES ........................................... 140 APPENDIX 144 viii LIST OF TABLES Table Page I. Chemical Composition of Ground Water from the Vamoosa-Ada Aquifer •••••••••••••••••• 39 II. Stream Observations and Chloride Concentrations 79 III. Chloride and Sulfate in Streams in the Oologah Reservoir Area ••••••••••••••••••••••..• 98 ix LIST OF FIGURES Figure Page 1. Location of the Verdigris River Basin in Kansas and Oklahoma . • . 2 2. Location of Verdigris River Basin in Oklahoma ••••.• 4 3. Rock Units That Outcrop in Hominy Creek Basin . 10 4. Rock Units that Outcrop in the Oologah Reservoir Area ................................... 13 5. Generalized Geologic Column of Coal •.•••••••••••••• 16 6. Potentiometric Surface and Aquifer Cross Sections of the Vamoosa-Ada Aquifer in Hominy Creek Basin....................................... 41 7. Oil and Gas Fields in Areas Studied in the Verdigris River Basin : •••••••••••••••••••• 47 8. Oil fields and Coal Field Activities in Fourmile Creek Basin . 55 9. Oil fields and Coal Field Activities in Lightning, Panther, and Plume Creek Basins 57 10. Oil fields and Coal Field Activities in Spencer Creek Basin . 58 11. Coal field Activities in Blue Creek Basin 60 12. Oil field and Coal Field Activities in Dog Creek Basin . • . 61 13. Precipitation-Weighted Mean of Chloride and Sulfate for 1982 ••••.•• ~.................... 67 14. Probability Graph of Chloride Analyses of Samples Collected on October 11 and 19, 1984 .••.••••••••• 69 15. Probability Graph of Sulfate Analyses of Samples Collected on October 11 and 19, 1984 ••••••.•••••• 70 X Figure Page 16. Chloride Concentrations at Streams Sampled on October 11, 1984 ................................ 71 17. Sulfate Concentratio~s at Streams Sampled on October 11, 1984 ................................ 72 18. Chloride Concentrations at Locations Sampled on October 19, 1984 . 74 19. Effects of Rainfall on Chloride Analyses at Control Stations in Hominy Creek Basin •••••••••••.•••••• 77 20. Probability Graph of Chloride Analyses From Samples Collected on November 4, 8, and 11, 1984 ••.•••••• 80 21. Chloride Concentrations at Locations in Hominy Creek Basin . 81 22. Probability Graph of Sulfate Analyses of Samples Collected on November 4, 8, and 11, 1984 ••••••••• 84 23. Sulfate Concentrations at Locations Sampled in Hominy Creek Basin . 85 24. Chloride Concentrations at Locations Sampled in Delaware Creek Basin ••••••••••••.•••••••••••• 87 25. Probability Graph of Chloride Analyses of Ground Water in Hominy and Delaware Creek Basins •••••••• 89 26. Probability Graph of Sulfate Analyses of Ground Water in Hominy and Delaware Creek Basins ••.••••• 91 27. Probability Graph of Chloride From Streams in Hominy Creek Basin During July 5-17, 1981 •••••••••.••..• 92 28. Chloride Concentrations at Streams in Hominy Creek Basin during July 5-15, 1981 •••••.••••••••••••••• 93 29. Rainfall at Claremore and Nowata