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Major and Trace Element Chemical Composition MAJOR AND TRACE ELEMENT CHEMICAL COMPOSITION OF GAHNITE FROM GRANITIC PEGMATITES AND A METAMORPHOSED MASSIVE SULFIDE DEPOSIT: SIGNIFICANCE FOR PEGMATITE FRACTIONATION AND DISCRIMINATION BETWEEN Li-RICH AND Li-POOR PEGMATITES by Jason Anthony Yonts July, 2014 Director of Thesis: Dr. Adriana Heimann Major Department: Geological Sciences Rare-element granitic pegmatites are common hosts to economic deposits of rare metals, including Li, Ta, and rare-earth elements, which are increasing in economic importance due to advancing technology. Gahnite (ZnAl2O4) occurs as an accessory mineral in metamorphosed massive sulfide deposits (MMSDs) and some rare-element granitic pegmatites, including those with rare-metal mineralization, but detailed chemical studies of gahnite in these rocks are very scarce. In this study, gahnite from twenty-four granitic pegmatites and the Broken Hill-type Nine Mile MMSD, Australia, was analyzed for major and trace element chemical compositions to determine the relative degree of evolution of the pegmatites and identify chemical differences between Li-rich and Li-poor pegmatites and between these and MMSDs. In the spinel ternary diagram in terms of mol % gahnite (Ghn), hercynite (Hc), and spinel (Spl) end-members, the compositions of gahnite from the pegmatites fall within the previously defined pegmatite field and are given by: Ghn70.63-98.48Hc0.95-28.61Spl0.00-4.52. Gahnite from the Nine Mile deposit (Ghn55.62-76.06Hc17.47-37.34Spl3.81-10.73) falls within the MMSD field characterized by compositions that reach higher Mg and lower Zn contents compared to gahnite from granitic pegmatites. Gahnite from the LCT (lithium, cesium, tantalum) family, rare-element class, beryl- columbite-phosphate subtype and LCT family, muscovite-rare element class, Li subclass granitic pegmatites of the Comechingones (Blanca Dora, Juan Román, Magdalena, La Ona, and Sin Nombre pegmatites) and Conlara (Nancy pegmatite) pegmatite districts, Pampean Pegmatite Province, Argentina, was analyzed in detail. The chemical composition of gahnite from these pegmatites is defined by the ranges Ghn78.49-90.35Hc9.07-20.52Spl0.25-3.37. Gahnite from the Nancy pegmatite has higher Mg and Mn contents than gahnite from the Comechingones pegmatites. Chemical zoning within gahnite crystals is characterized by an increase in Zn (~2.8 wt.% ZnO) and a decrease in Fe (~2.6 wt.% FeO) from core to rim, reflecting the evolution of the pegmatite melt via simple fractional crystallization. Plots of molecular Fe vs. Zn and Fe+Mg vs. Zn+Mn and Zn/Fe ratios in gahnite display the diadochy and the relative degree of fractionation of the pegmatites. The Zn/Fe ratios range from 3.82 to 9.96. Based on all these parameters, the relative degree of evolution of the pegmatites increases in the order: Sin Nombre → Magdalena → Juan Román → Blanca Dora → Nancy → La Ona. This order is consistent with mineralogical evidence and indicates that the composition of gahnite in granitic pegmatites can effectively be used to determine the relative degree of evolution of pegmatite melts. The trace elements present in gahnite are first-series transition metals (Ti, V, Cr, Co, Ni, and Cu), as well as Mn, Li, Ga, Cd, Sn, and Pb. Gahnite in the Nine Mile deposit reaches higher Ti, V, Cr, Co, Ni, and Pb and lower Mn, Li, Ga, Sn, and Cu contents than gahnite from granitic pegmatites. Gahnite from highly evolved granitic pegmatites of the Borborema Pegmatite Province, Brazil, has the highest Cu (up to 68 ppm), Mn (up to 8,819 ppm), Li (up to 376 ppm) and Zn (up to 43 wt.% ZnO) contents and these compositions may be good indicators of Li-rich pegmatites. This study shows that the major and trace element chemistry of gahnite in granitic pegmatites may be used to understand relative pegmatite evolution and to distinguish pegmatites that contain Li-mineralization from barren pegmatites. MAJOR AND TRACE ELEMENT CHEMICAL COMPOSITION OF GAHNITE FROM GRANITIC PEGMATITES AND A METAMORPHOSED MASSIVE SULFIDE DEPOSIT: SIGNIFICANCE FOR PEGMATITE FRACTIONATION AND DISCRIMINATION BETWEEN Li-RICH AND Li-POOR PEGMATITES A Thesis Presented To the Faculty of the Department of Geological Sciences East Carolina University In Partial Fulfillment of the Requirements for the Degree Master of Science in Geology by Jason Anthony Yonts July, 2014 © Jason A. Yonts, 2014 MAJOR AND TRACE ELEMENT CHEMICAL COMPOSITION OF GAHNITE FROM GRANITIC PEGMATITES AND A METAMORPHOSED MASSIVE SULFIDE DEPOSIT: SIGNIFICANCE FOR PEGMATITE FRACTIONATION AND DISCRIMINATION BETWEEN Li-RICH AND Li-POOR PEGMATITES by Jason A. Yonts APPROVED BY: DIRECTOR OF THESIS: ___________________________________________ (Dr. Adriana Heimann, PhD) COMMITTEE MEMBER: ___________________________________________ (Dr. Terri L. Woods, PhD) COMMITTEE MEMBER: ___________________________________________ (Dr. Eric M. Horsman, PhD) COMMITTEE MEMBER: ___________________________________________ (Dr. Michael A. Wise, PhD) CHAIR OF THE DEPARTMENT OF GEOLOGICAL SCIENCES: ___________________________________________ (Dr. Stephen J. Culver, PhD, DSc.) DEAN OF THE GRADUATE SCHOOL: ___________________________________________ (Dr. Paul J. Gemperline, PhD) ACKNOWLEDGEMENTS I would like to first thank my advisor, Dr. Adriana Heimann, for all of her help, support, and encouragement on this thesis project. I would also like to thank my other committee members, Drs. Eric Horsman, Terri Woods, and Michael Wise for all of their advice and knowledge on this project. Thank you to Tom Fink at East Carolina University Biology Department for help with SEM-EDS analysis and Nick Foster at Fayetteville State University for help with the EMP analysis. Alan Koenig at the USGS Denver LA-ICP-MS laboratory is thanked for help overseeing LA-ICP-MS analysis and providing advice for data interpretations. Thank you also to Michael Wise for providing expertise and helping to answer question about pegmatites. Also thanks to David London of the University of Oklahoma for providing expertise about pegmatites and to Miguel Galliski for providing samples of gahnite and information and assistance about pegmatites from Argentina. Samples of gahnite were also graciously provided by Dwight Soares, Adam Szuszkiewicz, Mike Wise, Wolf Leyh, the Smithsonian Institution in Washington, D.C., and George Harlow and Jamie Newman from the American Museum of Natural History, N.Y. Funding for this project was provided by the USGS Mineral Resources External Research Program (award G10AP00051) and the Thomas Harriot College of Arts and Sciences at East Carolina University and Research and Graduate Studies to Dr. Adriana Heimann. I thank the Society of Economic Geologists Hugh E. McKinstry Student Fund and Grant-in-Aid of Research from Sigma Xi, The Scientific Research Society, for providing funding for this project. I would also like to acknowledge funding from the East Carolina University Department of Geological Sciences and the Geological Society of America (GSA) student travel grant to attend and present my thesis research at the southeastern GSA conference in Blacksburg, VA. Finally, I would like to thank friends and family. Thank you to David Szynal, Erica Serna, Heather Lancaster, Leatha Moretz, and Katie Cummings for helping me in many ways during the last two years. I would have given up this endeavor if not for their moral support. Special thanks are due to my parents, Kay and James Yonts, and wife Megan Yonts for all of their love, support, and encouragement over the years making this chapter in my life possible. TABLE OF CONTENTS ACKNOWLEDGEMENTS ...................................................................................................... viii LIST OF TABLES .................................................................................................................... xii LIST OF FIGURES .................................................................................................................. xiii CHAPTER 1: THE COMPOSITION OF GAHNITE FROM THE COMECHINGONES AND CONLARA PEGMATITE DISTRICTS, PAMPEAN PEGMATITE PROVINCE, ARGENTINA: IMPLICATIONS FOR PEGMATITE FRACTIONATION ...................... 1 ABSTRACT ..................................................................................................................... 2 1.1 INTRODUCTION ..................................................................................................... 3 1.2 SAMPLING AND ANALYTICAL METHODS ...................................................... 4 1.3 GEOLOGIC SETTING ............................................................................................. 5 1.3.1 Conlara Pegmatite District ................................................................................ 6 1.3.1.1 Nancy Pegmatite ...................................................................................... 7 1.3.2 Comechingones Pegmatite District ................................................................... 8 1.4 CHARACTERISTICS OF GAHNITE ...................................................................... 10 1.5 GAHNITE CHEMISTRY .......................................................................................... 11 1.6 DISCUSSION ............................................................................................................ 13 1.6.1 Gahnite Formation and Occurrence .................................................................. 14 1.6.2 The Chemistry of Gahnite and Evolution of the Argentina Pegmatites ........... 15 1.6.3 Compositional Zoning of Gahnite ...................................................................
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