The behavior of molybdenum, tungsten, and titanium in the porphyry copper environment Item Type text; Dissertation-Reproduction (electronic) Authors Kuck, Peter Hinckley Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 08/10/2021 00:24:06 Link to Item http://hdl.handle.net/10150/565421 THE BEHAVIOR OF MOLYBDENUM., TUNGSTEN, AND TITANIUM IN THE PORPHYRY COPPER ENVIRONMENT Peter' 'Hinckley Kuck A Dissertation Submitted to the Faculty of the DEPARTMENT OF GEOSCIENCES. In Partial.Fulfillment of the Requirements. ' ■ For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College ■ THE UNIVERSITY OF ARIZONA 1 9 7 8 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE I hereby recommend that this dissertation prepared under my Peter Hinckley Kuck direction by ___________ , , The Behavior of Molybdenum, Tungsten, and Titanium entitled ________________________________________________________ in the Porphyry Copper Environment be accepted as fulfilling the dissertation requirement for the Doctor of Philosophy degree of _______________________________________________________ Dissertation Director Date As members of the Final Examination Committee, we certify that we have read this dissertation and agree that it may be presented for final defense. \ R A j r i A hi / 7IT 2 / 1 r 7 - Final approval and acceptance of this dissertation is contingent on the candidate's adequate performance and defense thereof at the final oral examination. STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at The University of Arizona and is deposited in the University Library to be made available to borrowers under rules of. the .Library. Brief quotations from this dissertation are allow­ able without special permission, provided that accurate ■ acknowledgment of source is made; Requests- for permission for extended quotation from or reproduction of this manu­ script in whole or in part may be granted by the head of the major department or the■Dean of the Graduate College when in his judgment the proposed: use of the material is in the interests of scholarship. In all Other instances, however,. permission must be obtained frOm the author. ACKNOWLEDGMENTS I am deeply indebted to Dr. Paul E. Damon for his supervision and support of this dissertation. Drs. John W. Anthony, John M. Guilbert, and John S. Sumner provided many helpful suggestions, comments, and constructive criticisms. I would.like to especially thank Dr. George W. Nelson fo r _his encouragement 'an d .invaluable.assistance . ■ • in many aspects of the project. Dr. Nelson, Dr. .Morton E . -. Hacks, and other members of the Nuclear Engineering;Depart- . ment irradiated more than one hundred mineral samples in the TRIGA reactor and allowed me to.use their gamma-ray . spectrometry system. It is a pleasure to express my appreciation to Robert B. Scarborough who assisted me in both the laboratory and the field. Dr. Muhammad Shafiqullah, Daniel J. Lynch, and the other members of the Laboratory of Isotope Geo- .chemistry kindly provided potassium^argon data on several mineralized intrusives. Dr. Denis L. Norton and Jerry E. Knight gave useful suggestions and assistance in con­ structing activity diagrams. Dr* Donald .Ev Livingston . provided constructive advice on x-ray fluorescence. Thomas M. Teska and Horton E. Newsom helped with the electron microprobe analyses. iv Michael H. Rauschkolb and his associates.-at AMAX Arizona, Inc. collaborated with me on the .examination of the copper-molybdenum-tungsten mineralization in the Twin Buttes ore body. Calvert D. lies of the Duval Sierrita Corporation provided samples and data on the mineralization at the Esperanza and Sierrita open pit mines. I would also like to thank the following individuals for their help: Janis K. Blainer, the late Thomas Breen, Dr. Donald M. Burt, J. L. Christman, .Richard. Graeme, Dr. Frederick T. , Graybeal , James Guthrie, Dr ^ Herbert E.- Hawke.s, Margo -Jennison, Peter L. Kresan, Norman E . Lehman, Richard Moore, Dr. Henn Oona, Dr. Eberhardt A. Schmidt, and Dr. Anne M. S'igleo. I owe a special debt of thanks to Dr. David L. Perry fdr: introducing me to the problems of molyb­ denite deposition. Mr. Henry G. Worsley, the owner of the Mary G mine, provided information on the mining history of the Las G.uij as and San Luis Mountains. The following mining companies - gave mb permission to. collect samples from their properties or provided samples for this study: ANAMAX . Mining Co., Cyprus Bagdad Copper Corp., Duval Sierrita Corp., Oracle Ridge Mining Partners, the Ray Mines Division of the Kehnecott Copper Corp., and the Phelps Dodge Corp. - .The editorial suggestions of Kathleen Roe Trevena were of great value and helped to make parts of the dis­ sertation smoother and clearer. Finally, I would like to ■thank Professor ter ah L„ Smiley, for his. valuable counsel and timely advice. Financial assistance was furnished in part by the National Science Foundation through a.summer traineeship and under Grant EAR?6-02590 to Paul E. Damon. TABLE OF CONTENTS Page LIST OF TABLES ................ ix ■ LIST OF ILLUSTRATIONS V . ... .... xii ABSTRACT ' . « . .... ......... .. xvi ■THE; MOLYBDENUM-TUNGSTEN' PROBLEM ;. 1 1.1 Differences in Behavior between Molyb­ denum and Tungsten • in Porphyry Copper Deposits . .... , . .1 1.2 Economic Implications of the Molybdenum- .. Tungsten- Problem . :. .. .. 5 1.3 Possible Explanations of the Difference in Behavior between Molybdenum and. Tungsten . 8 GEOCHEMISTRY OF MOLYBDENUM, TUNGSTEN, AND. TITANIUM . ... ... .............. 15 2.1. Differences in Electronic Structure . 15. 2.2 Effect of Differences in Nuclear Struc­ ture on the Abundances of the Three .. ■ Elements . .. ■.■. ..- . *■ . ....... 2 4 2 . 3 Molybdenum and Tungsten Minerals' .'., . .. 30 2.4 Laboratory Synthesis of Molybdates . and Tungstates . > . .40 MOLYBDENUM, TUNGSTEN, AND TITANIUM MINERALIZATION IN SOUTHERN ARIZONA . .. .... 49 3.1 Area of Investigation . ........ 49 3.2 Age Relationships . ...... 52 3.3 Types of Deposits . ..... 53 . 3.4 The Spatial Distribution of Molybdenite and Scheelite in Porphyry Copper Deposits and Related Skarns . ■. , . .. , . , . 57 3.5 . Rutile and Other Titanium-Bearing Minerals Associated with Chalcopyrite- Molybdenite Ores ... .. 68 vii . TABLE OF CONTENTS (Continued) Page CHEMICAL ANALYSES OF ORE MINERALS „ . 80 4.1 Preparation of Standards and .Samples . 80 4.2 Emission Spectrographic Analyses ......... 85 4.3 X-ray Fluorescence Analyses ....... 86 4.4 Neutron Activation Analyses . 87 DISCUSSION OF CHEMICAL ANALYSES . ...... 95 5.1 Minot Elements in Molybdenite . .' . 95 5.2 Rlienium,' Selenium, and Other Trace ' Elements- ' in Molybdeni te " . I . 98 : 5.3 Minor Elements in Wolframite . .114. ' ; 5.4 Scandium, Niobium, and Other Trace Elements in Wolframite . .. .- . 115 l 5.5 Minor and Trace Elements in Scheelite . 12 0 5.6 Tungsten> Copper, and Other Trace Elements in Rutile . ...... ' 127 TRANSPORT AND DEPOSITION OF MOLYBDENUM AND Tungsten , , . .. .. ..... , . 130 ■ 6.1 Transport Problems . a . .. »•. 130 6.2 The Solubility of Different Molybdenum and Tungsten Minerals in Hydrothermal Bf ine s ■' o . a . ;. e .- . * ■ e ‘ a . o . 0.0 e « « . « 132 . 6.3 Depositional Temperatures . 133 ; - 6.4 . Stable. Mineral Assemblages . ... .. 143 6.5 Activity-Activity Diagrams for the Ca—Fe—Cu—Mo—W—S—0—H System . 145 CONCLUSIONS \ . .. 163 APPENDIX A: COMPILATION OF 40K/4°Ar AGE DETERMINA­ TIONS OF LARAMIDE INTRUSIVES IN . SOUTHEASTERN ARIZONA THAT ARE ASSOCI­ ATED WITH COPPER-MOLYBDENUM OR COPPER- ' ■ ' TUNGSTEN MINERALIZATION: : . 1 . .. 167 • APPENDIX B: COMPILATION OF 40K/4°Ar AGE DETERMINAr- .. TIONS OF OLIGOCENE AND MIOCENE IN­ TRUSIVES IN SOUTHEASTERN ARIZONA . 176 APPENDIX C;' SEMIQUANTITATIVE EMISSION SPECTRO­ GRAPHIC ANALYSES OF MOLYBDENITE . 181 viii TABLE OF CONTENTS (Continued) Page APPENDIX D : EMISSION.SPECTROGRAPHIC ANALYSES OF . FERBERITE, WOLFRAMITE, AND HUEBNER- ITE . ' > .. ... 213 APPENDIX E : ' EMISSION SPECTROGRAPHIC ANALYSES OF SCHEELITE AND POWELLITE . 233 APPENDIX F : EMISSION SPECTROGRAPHIC ANALYSES OF : RUTILE, MAGNETITE, AND HEMATITE . ... 242 APPENDIX G :. CONVENTIONAL X-RAY FLUORESCENCE ANALYSES OF FERBERITE, . WOLFRAMITE, "■ AND HUEBNERITE ■ <, . „ . ... 2 51 APPENDIX.H : THERMODYNAMIC. PROPERTIES OF SELECTED MOLYBDENUM AND TUNGSTEN COMPOUNDS, , INCLUDING THE : DATA FOR THE MOLYBDATE. AND TUNG STATE ANIONS . ... 256 REFERENCES. CITED . ... o; ;. ... .. .. ... ... 26.0 LIST OF TABLES Table Page 1. Atomic properties of titanium, molybdenum, an cl ■ tungsten ». e & * « ». « # » -» o » » » » a » « 2 2. Molybdenum-tungsten isomorphism in por­ phyry copper deposits „ « i ° .• « - . .. • 3 3. Values of the Gibbs free-energy of formation for selected molybdenum and tungsten com^ pounds ».o. ................ 9 4. Electronic configurations of. the neutral Cl L- OXi-L £5 e O • e a a a a a -a a a a a a . ■ a a a a a a 1 2 5. Deviations In atdmic orbital filling . 18 . 6. Various covalent, ionic,.and.metallic radii for titanium, molybdenum, and: tungsten. ^ . 22 7» The partial ionic character of different - • bonds formed by titanium, molybdenum, and tungsten a a a a a a a , a O' a a . a a a . a a - a -a ■ a a 2 3 8 a The concentration