TEPHROCHRONOLOGY AND STRATIGRAPHY OF EOCENE AND OLIGOCENE VOLCANIC ASHES OF EAST AND CENTRAL TEXAS A Thesis by MINDI HEINTZ Submitted to the Office of Graduate Studies and Professional Studies of Texas A&M University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Chair of Committee, Thomas E. Yancey Co-Chair of Committee, Brent V. Miller Committee Member Deborah J. Thomas Head of Department, John R. Giardino December 2013 Major Subject: Geology Copyright 2013 Mindi Heintz ABSTRACT Sedimentary formations of east and central Texas contain many Eocene to Oligocene volcanic ash beds, with some of the younger ash layers containing hydrated but otherwise unaltered glass shards. This study analyzed samples of 15 volcanic ash beds using neutron activation analysis (NAA) of bulk ash and glass shards, inductively coupled plasma mass spectrometry (ICPMS) of bulk ash, and electron microprobe analysis of both apatite phenocrysts and glass shards to characterize their geochemistry. 40Ar/39Ar dating of single sanidine phenocrysts gives an age of 30.64 ±0.03 Ma for the youngest (Sam Rayburn) sample to 41.79 ±0.02 Ma for the oldest (Hurricane Bayou) sample. The nine radiometric dates obtained by this study serve to better constrain the ages of the Claiborne and Jackson Groups and the Catahoula Formation of Texas with the Conquista and Hurricane Bayou ash beds being possible calibration points for the Eocene/Oligocene and Lutetian/Bartonian boundaries, respectively. Geochemical fingerprinting, particularly apatite phenocryst chemistry, supports the correlation of the Little Brazos volcanic ash in Brazos County to volcanic ash deposits in Houston County, Texas, and provides supporting evidence for equivalence to the St. Johns bentonite in Louisiana. Geochemical fingerprinting also suggests equivalence of the Caddell (Koppe Bridge) volcanic ash to deposits within the Gonzales County bentonite mines of south-central Texas. Major element electron microprobe data from seven samples of volcanic glass shards indicate the ash was produced from sub-alkaline rhyolitic volcanism and the ii trace-element characteristics of all 15 ashes are consistent with subduction-related sources. Rare earth element (REE) data indicates light rare earth element (LREE) enrichment with a moderate Europium anomaly. The Sierra Madre Occidental of Mexico is the likely source area, but the Trans-Pecos of Texas and Mogollon-Datil of New Mexico cannot be definitively ruled out as possible eruptive source regions. iii DEDICATION I would like to dedicate this work to my loving husband, Colby Kreft, who put up with geologic journal papers being scattered all over the house for two years and to my family and friends for being so supportive. iv ACKNOWLEDGEMENTS I would like to thank my committee chair, Dr. Yancey, and my committee co- chair, Dr. Miller, and member, Dr. Thomas for their guidance and support throughout the course of this research. Dr. Yancey’s vision of the project and Devon Energy’s funding for graduate student support are what made this research and my master’s degree possible. I would also like to thank Dr. Guillemette for his expertise on the electron microprobe that made my apatite analysis a success. Thanks also go to my friends and colleagues and the department faculty and staff for making my time at Texas A&M University a great experience. I would also like to acknowledge all the geologists that have helped me along the way, especially, Dr. Christopher Baldwin, Dr. Brian Cooper and Dr. David James. Finally, thanks to my mother and father for their encouragement and to my husband for his patience and support. v TABLE OF CONTENTS Page ABSTRACT ....................................................................................................................... ii DEDICATION .................................................................................................................. iv ACKNOWLEDGEMENTS ............................................................................................... v TABLE OF CONTENTS .................................................................................................. vi LIST OF FIGURES ........................................................................................................ viii LIST OF TABLES ............................................................................................................. x INTRODUCTION .............................................................................................................. 1 PALEOGENE VOLCANIC ASH DEPOSITS OF EAST AND CENTRAL TEXAS ...... 7 METHODS ....................................................................................................................... 14 40Ar/39Ar Dating ........................................................................................................... 14 Neutron Activation Analysis (NAA)............................................................................ 15 Electron Microprobe Analysis of Volcanic Glass Shards ............................................ 15 Electron Microprobe Analysis of Apatite Phenocrysts ................................................ 16 Inductively Coupled Plasma Mass Spectrometry (ICPMS) Analysis .......................... 17 RESULTS ......................................................................................................................... 19 Elemental Chemistry of Volcanic Ash Deposits .......................................................... 19 Bulk Volcanic Ash Chemistry .................................................................................. 19 Volcanic Glass Shard Chemistry .............................................................................. 29 Apatite Phenocryst Chemistry .................................................................................. 37 40Ar/39Ar Dating ........................................................................................................... 39 DISCUSSION .................................................................................................................. 42 40Ar/39Ar Dating ........................................................................................................... 42 Correlation of Volcanic Ash Beds ............................................................................... 43 Patterns of Volcanic Ash Alteration............................................................................. 51 Possible Source of Volcanic Ash ................................................................................. 56 vi Page CONCLUSIONS .............................................................................................................. 60 REFERENCES ................................................................................................................. 62 APPENDIX A .................................................................................................................. 70 vii LIST OF FIGURES Page Figure 1. Location of volcanic ash samples ..................................................................... 2 Figure 2. Stratigraphy for the study location showing the position of the volcanic ash beds studied in this report ............................................................ 3 Figure 3. Silicic volcanism trend running from Mexico into the western United States that makes up the Sierra Madre Occidental, Trans-Pecos Volcanic Province and Mogollon-Datil Volcanic Field ................................... 5 Figure 4. Examples of volcanic ash deposits ................................................................... 8 Figure 5. TAS diagram showing Na2O + K2O versus SiO2 data from the ICPMS bulk volcanic ash analysis .............................................................................. 24 Figure 6. Trace element data from ICPMS analysis of bulk volcanic ash samples ....... 25 Figure 7. REE data from ICPMS analysis of bulk volcanic ash .................................... 26 Figure 8. Plot of La/Yb versus Yb showing the measure of the degree of REE fractionation with changing REE content in bulk volcanic ash data from ICPMS analysis .................................................................................... 27 Figure 9. Plot of La/Sm versus Sm showing the degree of LREE fractionation with changing REE content in bulk volcanic ash from ICPMS analysis ....... 28 Figure 10. BSE images showing the South Somerville, Conquista and Tarball Quarry volcanic glass separates ..................................................................... 30 Figure 11. Alkali data plotted versus total wt % for the South Somerville and Tarball Quarry individual glass shard analyses .............................................. 31 Figure 12. TAS diagram showing Na2O + K2O versus SiO2 data from the seven glass bearing volcanic ashes ........................................................................... 33 Figure 13. Trace element data from NAA of volcanic glass shards ................................ 35 Figure 14. REE data from NAA of volcanic glass shards ............................................... 36 viii Page Figure 15. Plot of Mg versus Mn versus Cl from individual apatite microprobe analysis ........................................................................................................... 38 Figure 16. Summary of age probability data presented in stratigraphic order from youngest to oldest ........................................................................................... 41 Figure