REVieWS IN EConomiC Geology Volume 7 APPLICATIONS OF MICROANALYTICAL TECHNIQUES TO UNDERSTANDING MINERALIZING PROCESSES CONTENTS PART I: GEOCHRONOLOGY AND RADIOGENIC ISOTOPES U-Th-Pb Geochronology by Ion Microprobe I.S. Williams ICP Multiple-Collector Mass Spectrometry A.N. Halliday, J.N. Christensen, D.-C. Lee, C.M. Hall, and In Situ High-Precision Isotopic Analysis C.J. Ballentine, M. Rehkamper, W. Yi, X. Luo, and D. Barfoo 40Ar/39Ar Geochronology Using the Laser Microprobe K .V. Hodges PART II: STABLE ISOTOPES Ion Microprobe Analysis of Oxygen, J.W. Valley, C.M. Graham, B. Harte, J.M. Eiler, and P.D. Kinny Carbon, and Hydrogen Isotope Ratios Laser Microanalysis of Silicates for 18O/17O/16O and of D. Rumble and Z.D. Sharp Carbonates for 18O/16O and 13C/12C Ratios Sulfur Isotopes by Ion Microprobe M.A. McKibben and L.R. Riciputi Sulfur Isotope Analyses Using the Laser Microprobe W.C. Shanks, III, D.E. Crowe, and C. Johnson PART III: ELEMENTAL ANALYSIS Ion-Microprobe Quantification of Precious Metals in Sulfide Minerals A.C.L. Larocque and L.J. Cabri Micro-PIXE in Earth Science J.L. Campbell and G.K. Czamanske Economic Applications of Accelerator Mass Spectrometry G.C. Wilson Major, Trace, and Ultratrace Element Analysis by Laser Ablation ICP-MS W.I. Ridley and F.E. Lichte PART IV: FLUID INCLUSIONS Evidence for Sources of Salinity and Dissolved Gases, Fluid Mixing and J.J. Irwin Phase Separation, from Laser Microprobe Analysis of Cl, K, Br, I Ar, Kr, and Xe in Fluid Inclusions The Laser Raman Microprobe as a Tool for the Economic Geologist J.D. Pasteris Synchrotron-Source X-ray Fluorescence Microprobe: D.A. Yanko and J.A. Mavrogenes Analysis of Fluid Inclusions Editors M.A. McKibben, W.C. Shanks, III, and W.I. Ridley SOCIETY OF ECONOMIC GEOLOGISTS, INC. Society of Economic Geologists, Inc. Reviews in Economic Geology, Vol. 7 Applications of Microanalytical Techniques to Understanding Mineralizing Processes M.A. McKibben, W.C. Shanks, III, and W.I. Ridley, Editors Additional copies of this publication can be obtained from Society of Economic Geologists, Inc. 7811 Shaffer Parkway Littleton, CO 80127 www.segweb.org ISBN: 978-1-629495-65-1 The Authors: Louis J. Cabri Frederick E. Lichte W.C. Shanks, III CANMET U.S. Geological Survey U.S. Geological Survey 555 Booth Street Denver Federal Center Branch of Geochemistry Ottawa, Ontario KIA OGI Box 25046, Mail Stop 973 973 Denver Federal Center Canada Denver, CO 80225 Denver, CO 80225 Tel. +1.613.995.4073 USA USA Fax +1.613.996.9673 Tel.+ 1.605. 787.6837 Tel.+ 1.303.236.2497 email: [email protected] email: [email protected] Fax +1.303.236.3200 email: [email protected]. usgs.gov lain Campbell John A. Mavrogenes University of Guelph Research School of Earth Sciences Zachary D. Sharp U.C. 4th Floor The Australian National University Department of Earth and Guelph, Ontario NIG 2Wl Canberra, A.C.T. 0200 Planetary Sciences Canada Australia Northrop Hall Tel. +1.519.824.4120 ext. 3846 Tel. +011.61.249.3416 University of New Mexico Fax +1.519.767.1693 Fax +011.61.249.5989 Albuquerque, NM 87131 email: jlc@physics. uoguelph.ca email: [email protected] USA Tel.+ 1.505.277.2000 G.K. Czamanske Michael A. McKibben Fax +1.505.277.8843 750 W. Greenwich Place Department of Earth Sciences email: [email protected] University of California Palo Alto, CA 94303 USA Riverside, CA 92521 John W. Valley Tel. +1.650.328.7153 USA Department of Geology and Geophysics email: [email protected]. usgs.gov Tel.+1.909.787.3444 University of Wisconsin-Madison Fax+1.909.787.4324 Madison, WI 53706 Alex N. Halliday email: [email protected] USA Department of Geological Sciences Tel. + 1.608.263.5659 University of Michigan Jill Dill Pasteris Fax +1.608.262.0693 2534, C.C. Little Building Department of Earth and email: [email protected] Ann Arbor, MI 48109-1063 Planetary Sciences USA Washington University David A. Yanko Tel+1.13.764.1482 1 Brookings Drive, Campus Box 1169 Department of Geology Fax +1.313.763.4690 St. Louis, MO 63130-4899 Georgia State University email: [email protected] USA P.O. Box 4105 Tel.+1.314.935.5434 Atlanta, GA 30302-4105 Kip Hodges Fax +1.314.935.7361 USA Massachusetts Institute of Technology email: [email protected] Tel. +1.404.651.2272 Cambridge, MA 02139 Fax +1.404.651.1376 USA W. Ian Ridley email: [email protected] Tel. + 1.617.253.2927 U.S. Geological Survey Fax + 1.617.253.6735 Denver Federal Center Ian S. Williams email: [email protected] Box 25046, MS 973 Geochronology and Isotope Geochemistry Denver, CO 80225 Research School of Earth Sciences J.J. Irwin USA The Australian National University Cadence Mineral Resources Inc. Tel. + 1.303.236.5558 Canberra, ACT 0200 2658 Bellevue Avenue Fax +1.303.236.3200 Australia West Vancouver, BC V7V 1E4 email: [email protected] Tel. +011.61.2.6249.5164 Canada Fax +011.61.2.6279.8345 Tel. + 1.604.644.6515 Lee Riciputi email: [email protected] Fax +1.604.683.2235 Oak Ridge National Lab email: [email protected] P.O. Box 2008 Graham C. Wilson Oak Ridge, TN 37831-6365 IsoTrace Laboratory Adrienne Larocque USA University of Toronto Department of Geological Sciences Tel. +1.423.576.4839 60 St. George Street University of Manitoba Fax +1.423.576.8559 Toronto, Ontario M5S IA7 125 Dysart Rd. email: [email protected] Canada Winnipeg, MB R3T 2N2 Tel. +1.416.466.3386 Canada Douglas Rumble Fax+1.416.978.4711 Tel. +1.204.474.7413 Geophysical Laboratory email: [email protected]. utoron to.ca Fax + 1.204.47 4. 7623 5251 Broad Branch Rd., NW email: [email protected] Washington, D.C. 20013-1305 USA Tel. + 1.202.686.2410 ext. 2483 Fax +1.202.686.2419 email: [email protected] 11 PREFACE Recent technological advances have made possible the This volume, like the course, is divided into four topical sampling and geochemical analysis of increasingly smaller sections: Geochronology and Radiogenic Isotopes, Stable masses of crystalline material. The application of these Isotopes, Elemental Analysis, and Fluid Inclusions. Each new microanalytical te chniques to minerals and rocks chapter represents an overview of the technique utilized opens up a level of detailed geological information that and its practical applications to understanding mineral­ was heretofore masked by more primitive bulk sampling and rock-forming processes. It is clear that some tech­ techniques. We can now conduct in situ sampling and niques are further along than others in terms of specific analysis of individual growth bands within crystals, and of applications, but all of them are promising and have high tiny solid and fluid inclusions trapped within crystal lat­ potential fo r making important contributions to geologic tices, in many cases determining not only their composi­ knowledge. We hope that the volume makes members of tion but also their time of fo rmation. the geologic community more aware of the microanalyti­ Because of these advances and their potential for assist­ cal techniques and the potential applications to their own ing scientists in attaining a better understanding of min­ specific geologic research problems. eralizing processes, the Society of Economic Geologists The conveners and editors are indebted to all of the au­ held a short course in October 1996 to highlight the di­ thors for their timely efforts in the production of the short verse applications of these techniques. Attended by more course and the resulting volume. than 85 people at The Nature Place Resort in Florissant, Colorado, the course brought together scientists from Australia, Europe, North America, and South Mrica. It was Michael A. McKibben the largest short course ever held by the SEG in conjunc­ W.C. (Pat) Shanks, III tion with a GSA annual meeting. W. Ian Ridley iii BIOGRAPHIES LOUIS J. CABRI is principal scientist at Canada Centre for multiple collector inductively coupled plasma mass spectrome­ Mineral and Energy Technology, Ottawa, and has performed try and its application to the origin and early history of the research in mineralogy applied to ores and characterization of solar system, studies of crustal fluid flow, and paleoceanogra­ various industrial wastes over the past 34 years. He has been in­ phy. volved in the development of new microanalytical techniques for surface analysis and trace-element analyses of minerals, es­ K. V. HODGES is a professor of geology and Dean for pecially for precious metals. Cabri has also been a consultant Undergraduate Curriculum at the Massachusetts Institute of on trace-element analytical techniques and mineralogical bal­ Technology. He received his B.Sc. from the University of North ances, for base metals, gold, silver, and platinum-group ele­ Carolina in 1978 and his Ph.D. from the Massachusetts ment ores, to industry, governments, and universities, on an Institute international level. His work has been published in 145 peer­ of Technology in 1982. Much of his research focuses on the reviewed journals, and he is the winner of SEG Lindgren relationships among thermal, deformational, and erosional award in1965, the Mineralogical Association of Canada's Past­ processes during the evolution of mountain ranges. In the field 4 Presidents' Medal, and the Leonard G. Berry Medal. Cabri is a of 0Arj39Ar thermochronology, recent projects include ex­ fellow of the Royal Society of Canada, Academy of Sciences. ploring the time-temperature histories of metamorphic com­ plexes in the Himalaya, East Greenland Caledonides, Irish J. L. (lAIN) CAMPBELL is a professor of physics at the Caledonides, and the southwestern United States.