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Produced by the NASA Center for Aerospace Information (CASI) t UNIVERSITY OF HAWAII (NASA-CR-175763) LE FIC'IEAI fifLKIANCI CE NE5-15973 CIBSObATE MIbkBJ1! AIL cCCFL IA M VISMI A6L NIA& 1NF8AB11; I,„. =5 - 2.!E MICRONS) Ahr. ITS APPLICATICNf IN CIPEENAIT FETFOLCGY UnclaE (6awaii Uciv., Ectclulu.) 256 F G3/46 2 12 12 GD V U ? CO '+ C) y 9x a Planetary Ceosciences Division HAWAII INSTITUTE OF GEOPHYSICS 2525 CORREA ROAD • HONOLULU, HAWAII 96822 808 -948-6488 is s SPECTRAL. REFLECTANCE OF CARBONATE MINERALS AND ROCKS IN THE VISIBLE AND NEAR INFRARED (0.35 to 2.55ym) AND ITS APPLICATIONS IN CARBONATE PETROLOGY 8 6 9 0 SPECTRAL REFLECTANCE OF CARBONATE MINERALS AND ROCKS IN ISE VISIBLE AND NEAR INFRARED (0.35 to 2.53µm) AND ITS APPLICATIONS IN CARBONATE PETROLOGY A DISSERTATION SUBMITTED TO IBE GRADUATE DIVISION OF THE UNIVERSITY OF HAWAII IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN GEOLOGY AND GEOPHYSICS AUGUST 1984 By Susan Jenks Gaffey Dissertation Committee Bernard Ray Hawke, Chaiman Thomas B. McCord Pow— Foong Fan Ko st Pankiw sky j Fred T. Mackenzie George Andermann, Outside Member I i We certify that we have read this dissertation and that in our opinion it is satisfactory in scope and quality as a dissertation for the degree of Doctor of Philosophy in Geology and Geophysics. DISSERTATION CM11TTEE 0 Chairman f V Y // I Ir .f t' ACnrvWLEGENDM a Funding for this work was provided by Jet Propulsion Laboratory Grant JPL #956370, by NASA Grant NSG #7312. and b4 C aylord, Leonard, and Edna Cobeen. f Mineral samples were kindly provided by tit Smithsonian, by john Fuller of the British Museum. by George McCormick at the Geology Depart- ment, University of Iowa, and by Milton Manhoff, president of the Rock and Mineral Society of Hawaii. Fritz Thayer, of the Hawaii Institute of Geophysics, University of Hawaii at Manoa. provided samples of coccolith and foram oozes. Samples of calcareous ooze, chalk, and limestone were f^ I provided by the Deep Sea Drilling Project. I i i I would like to thank Edith Jenks, Michael Gaffey, Debbie Craven, S and Mark Rognstad for their assistance in the field. X-ray fluorescence analyses were provided by John Sinton, Kevin Reed performed the chemical analyses by spark spectrometery and atomic absorption spectrophotometry, and assisted with the X-ray diffraction analyses. Virginia Greenberg provided valuable advice on these analyti- cal techniques. Karen Margolis assisted with the SEM photography and EDAZ analyses. I would like to thank John Adams at the Unversity of Washington Y and Robert Huguenin at the Center for Remote Sensing at the University of Massachusetts at Amherst for allowing me to use their reflection spectrophotometers and computer facilities. - iii - M wr TV t \^., Ted Roush wrote the program which translates data from the Univer- sity of Washington instrument to our format. Pam Blake devised the method by which laboratory spectra were convolved to TM and SMIRR band passes. I would like to thank Bob Singer and Pam Blake for helpful dis- cussions of the realities of remote sensing. No one completes work for a degree without the assistance of teach- ers, fellow students. staff, family, and friends. I've been particu- larly fortunate in this regard and would like to express my gratitude to the many nice folks who've helped me along, the wny. Special thanks to Bob Huguenin who first suggested this project and provided many of the samples used. His continuing interest and encouragement, and his helpful discussions of the work are greatly appreciated. Thanks also to Tom McCord who encouraged me to . return to graduate school, served as my advisor during my first years back, had the courage to let me do my own thing, and even found research funds with which to do it. I also want to thank Ray Hawke who took over as my advisor when he joined the graduate faculty. He is most truly a gentleman and a scho- lar, and his guidance and help are greatly appreciated. Many thanks al.o to my other committee members, Seymour Schlanger, Pow-Foong Fan, Bost Pankiwskyj, George Andermann, and Fred Mackenzie, for their help and encouragement. I'd like to thank the many people at PGD who holped an old-style soft-rocker learn to cope with computers and stater-of-the-art equipment: Lucy McFadden, Bob Singer, Roger Clark, Mark Rognstad, Jeff Bos.el, and Rodney Kam. Special thanks to Pam Qwensby who initiated me into the mysteries .. f GFIT. - iv - I Thanks to all the PGD grads who've helped make this a pleasant and fruitful place to work: Lucy, Jeff B., Paul, Bob B., Ted, Ed. Aaron, Marci, Stevv, with special aloha for Pam b., Chuck, and Lisa, fellow— residents of the terrestria! ghetto. { Mahalo to our engineers, Mark Rognstad, Karl Hinck, Jeff Bosel and Wendy Harrison who make things run, keep than+ running, and then get them running again. Your services above and beyond the call of duty during crashes, equipment failures, and the recent air— conditioning crisis are greatly appreciated by all. I'd also like to thank our user— friendly, scientist—compatable t. live-,*are — Jeff Hoover, Graham Bromley, Rodney gam, Duncan Chesley, and Tim Jackowski. Thanks also to Sam. Zany, Thomas. Phil. and all the other staff and admin people who make this place ran. I'd like to express special thanks to Kevin Reed. His persistence in the face of all the administrative hassles and bureaucratic red tape the University is able to generate, and his success in coping with the "kitchenette" dererve special mention. I particularly want to express my gratitude tc my mother. She's been in this with me since my Girl Scout rock badge -• mother, source of funds, chaffeur, able field assistant, and very special friend. This is her degree. too. Last, I want to thank my husband Mike, for sharing his knowledge of spectroscopy with me, and for sharing his life with me. I couldn't have done this without his encouragement, his support and his love. He mad6 the impossible possible. I. — v — ANSTner Reflection spectroscopy in the visible and near infrared (0.35 to 2.55µm) offers a rapid, inexpensive, nondestructive tool for determining the mineralogy and investigating the minor element chemistry of the hard-to-discriminate carbonate minerals, and can, in one step, provide information previously obtainable only by the co-sbined application of two or more analytical techniques. When light interacts with a mineral certain wavelengths are preferentially absorbed. The number, positions, widths and relative intensities of these absorptions are diagnostic of the mineralogy and chemical composition of the sample. At least seven bands due to vibrations of the carbonate radical occur between 1.60 and 2.55µm. Positions of these bands vary from one carbonate mineral to another and can be used for mineral ide tification. Cation mass is the primary factor controlling band position; cation radius plays a secon- dary role. Electronic processes in the d-shells of transition metal cations can also cause absorptions. Absorbing species in carbonate minerals include Fe 2Y , 1Mn2+ , Ni2+ . Co2+ , and Cut+ . Fe2+ bands are centered near 1.1µm. They vary in width, position. and shape from one calcite group mineral to another, reflecting differences in the size and symmetry of the octahedral sites in these minerals, and can aid in mineral identifi- cation. Relative intensities of transition metal absorptions increase with increasing cation abundance, and can be used to determine cation concentrations. Detection limits for Ma 2+ are about 0.10 weight per 2+ cent hfa, for Fe about 0.01 weight per cent Fe, and for Cu + about 0.005 weight per cent Cu. Positions of carbonate bands may also vary with variations in chemical composition. - vi - ^' i k z.-I Absorption features due to water may also occur in spectra of car- bonate samples. Liquid water has two strong absorptions near 1.4µm and 1.9µm. Absorptions due to water bound in clays are narrower and occur at shorter wavelengths than those due to liquid water. OH produces absorptions near 1.4µm and 2.2µm, but the 1.9µm feature is lacking. Absorptions due to water bound in hydrated carbonate minerals phases are ;t broader and occur at longer wavelengths than those due to liquid water. Spectra indicate that hydrozincite and hydrocerussite. believed to con- tain only OH actually contain bound H 2 O as well. Spectra indicate that aqueous fluid inclusions are nearly ubiqui- tons in carbonate rocks and minerals, and are particularly abundant in k skeletal material. The quantity of inclusions varies from one type of organism to another, with coccoliths and planktonic forams containing the least water, corals and coralline algae containin the most.