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Geochemical Characterization of Sulfide Mineral Weathering For Geochemical characterization of sulfide mineral weathering for remediation of acid producing mine wastes by Stuart Russell Jennings A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Land Rehabilitation Montana State University © Copyright by Stuart Russell Jennings (1993) Abstract: The generation of acid mine drainage as a consequence of sulfide mineral oxidation is a widespread source of resource degradation. The objective of this investigation was to evaluate the influence of sulfide mineral weatherability on acid generation processes. In addition to acid generation by pyrite, the weathering characteristics of common sulfide minerals was investigated and correlated to detection by acid-base account (ABA) methodologies. The influence of particle morphology, and not particle size, was found to exert the dominant control on mineral weathering processes. Massive morphology particles generated acid at a significantly greater rate than euhedral morphology samples. Acid generation was a consequence of mineral dissolution which occurred nonuniformly across the surface of minerals during oxidation. Mineral surface weathering occurred at sites of excess energy including grain edges, steps, defects, microcracks and inclusions, resulting in the formation of etch pits. Massive morphology particles exhibited the greatest density of crystalline defect, and had the greatest rate of oxidation. Sulfide minerals found to be acid generating, in addition to pyrite, include marcasite, pyrrhotite, arsenopyrite, chalcopyrite and sphalerite. Minerals containing sulfur in the atomic structure which were not acid producing include barite, anhydrite, gypsum, anglesite, jarosite, chalcocite and galena. Delineation of acid producing and nonacid producing sulfur forms by ABA extraction methods, a standard operating procedure used in the United States, was determined to be ineffective. Effective mineral classification, particle morphology identification and observation of mineral weathering processes were accomplished by scanning electron microscopy. Accurate assessment of sulfur form distribution and sulfide mineral weathering characteristics are required for effective remediation of sites impacted by mining. GEOCHEMICAL CHARACTERIZATION OF SULFIDE MINERAL WEATHERING FOR REMEDIATION OF ACID PRODUCING MINE WASTES by Stuart Russell Jennings A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Land Rehabilitation MONTANA STATE UNIVERSITY Bozeman, Montana September 1993 APPROVAL of a thesis submitted by Stuart Russell Jennings This thesis has been read by each member of the thesis committee and has been found to be satisfactory regarding content, English usage, format, citations, bibliographic style, and consistency, and is ready for submission to the College of Graduate Studies. Chairperson, Graduate Com Approved for the Major Department )3 i<m ( Iohn \yrihf)J)(n\_____ Dati ' Head, Major Department Approved for the College of Graduate Studies 1 7 Date Graduate Dean iii STATEMENT OF PERMISSION TO USE In presenting this thesis in partial fulfillment of the requirements for a master’s degree at Montana State University, I agree that the Library shall make it available to borrowers under rules of the Library. If I have indicated my intention to copyright this thesis (paper) by including a copyright notice page,.copying is allowable only for scholarly purposes, consis­ tent with "fair use" as prescribed in the U.S. Copyright Law. Requests for permission for extended quotation from or reproduction Of this thesis in whole or in parts may be granted only by the copyright holder. Signature 7 Date iv ACKNOWLEDGEMENTS . I wish to extend my thanks to the many coal and metal mines unnamed, in this report, which provided valuable insight and sample material for use in research. I thank my graduate committee, comprised of Dr. Douglas Dollhopf, Mr. Dennis Neuman, and Dr. Bill Inskeep, for their technical guidance. Special thanks are also bestowed upon Dawn Major for her tireless efforts at the comput­ er. Appreciation is extended to current and former land rehabilitation graduate students Don Dahlgren, James Poell and Bryce Romig. Thanks are also extended to Dr. Dick Lund for his invaluable guidance on statistical methods, and to Kathrin Olson-Rutz for her assistance with computer statistical" software. Comput­ er graphic assistance was provided by Bill Moody. Electron microprobe analyses were performed by Dr. David Mogk who provided essential data and interpreta­ tion of sulfide mineral nonhomogeneity. Mineral processing and scanning electron microscopy was performed at Montana Tech under the supervision of. Dr. Vern . Griffith and Bill Huestis who provided conscientious guidance and steady support throughout the project. TABLE OF CONTENTS Page ACKNOWLEDGEMENTS .............................................................................................. iv TABLE OF CONTENTS...................... v LIST OF T A B L E S.................................................................................................. viii LIST OF F IG U R E S............................................................................................................. x ABSTRACT ........................... xiii IN TR O D U C TIO N ................................................................. I Study Objectives.......... ............................................................................................... 3 LITERATURE REVIEW ................................................................................................ 4 tj - Pyrite Formation, Particle Size And Morphology i n v o Sedimentary Pyrite F orm ation............................... Igneous Pyrite Formation ...................................... Iron-Sulfur Mineral Chemistry.......... .................... on Acid Mine Drainage ................................................ Mineral Dissolution And Surface Chemistry..................................................... 14 N eutralization................................................................................................ 16 DESCRIPTION OF MINERALS USED IN THIS INVESTIGATION .......... 20 Identification Of Minerals Obtained From Operational Mines . ............. 20 Identification Of Pure Mineral Samples By S o u rce......................................... 25 THE INFLUENCE OF PARTICLE SIZE AND MORPHOLOGY ON SULFIDE MINERAL W EATH ERABILITY.............................................. 27 Acid Generation By Sulfide Mineral Oxidation............... v ........................... 27 M eth o d s.................................................................................................. ................ • 29 Sample preparation ......................................................................................... 29 Particle Morphology Identification ........................... 31 Sample Oxidation by 10% H2O2 ........................... 31 Sample Examination By Scanning Electron Microscopy....................... 32 Examination of Surface Weathering Processes by SEM . ..................... 33 Water Weathering of Pyrite .................................................................... .. 33 vi TABLE OF CONTENTS—Continued Page Particle Morphology Identification...................................................................... 34 Particle Morphology Identification by S E M .............................................. 37 Acid-Base Account Of Natural Sam ples............................................................. 41 Weatherability Of Sulfide Minerals By Oxidation With Hydrogen Peroxide 42 Sulfide Mineral Mass Change After Weathering .................................... 45 Sulfide Mineral Leachate pH After Weathering ...................................... 51 Sulfide Mineral Leachate Electrical Conductivity After Weathering . 53 Sulfide Mineral Leachate Iron Content After W eathering.................. 56 Sulfide Mineral Leachate Sulfate Content After W eathering............. 58 Sulfide Mineral Leachate Titratable Acidity After W eathering.......... 60 Sulfide Mineral Reaction Time During Oxidation ............................ .. 64 Weatherability of Different Sulfide Mineral Morphologies.................. 67 Stoichiometric Balance of Pyrite O xid ation .............................................. 74 SEM/EDAX Examination Of Weatherability Of Different Pyrite Morphologies ......................................................................... 79 Oxidation Of Pyrite By Deionized W ater .......................................................... 97 Mass Change .................................................... 97 Leachate pH ..................................................................................................... 99 Leachate Electrical Conductivity............................................................... 100 Leachate Iron ................................................................................................ 100 Leachate Sulfate ........................................................................................... 100 Leachate Titratable Acidity......................................................................... 101 D iscussion........................................................................................................ 102 ACID PRODUCTION FROM DIFFERENT SULFUR BEARING MINERALS DURING O X ID A T IO N ..................................................................... 106 Distribution Of Sulfur Minerals
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