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Spectral mineralogy of terrestrial planets: scanning their surfaces remotely
- Roger G. Burns
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- Journal:
- Mineralogical Magazine / Volume 53 / Issue 370 / April 1989
- Published online by Cambridge University Press:
- 05 July 2018, pp. 135-151
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Spectral measurements of sunlight reflected from planetary surfaces, when correlated with experimental visible-near-infrared spectra of rock-forming minerals, are being used to detect transition metal cations, to identify constituent minerals, and to determine modal mineralogies of regoliths on terrestrial planets. Such remote-sensed reflectance spectra measured through earth-based telescopes may have absorption bands in the one micron and two micron wavelength regions which originate from crystal field transitions within Fe2+ ions. Pyroxenes with Fe2+ in M2 positions dominate the spectra, and the resulting 1 μm versus 2 µm spectral determinative curve is used to identify compositions and structure-types of pyroxenes on surfaces of the Moon, Mercury, and asteroids, after correcting for experimentally-determined temperature-shifts of peak positions. Olivines and Fe2+-bearing plagioclase feldspars also give diagnostic peaks in the 1 µm region, while tetrahedral Fe2+ in glasses absorb in the 2 µm region as well. Opaque ilmenite, spinel and metallic iron phases mask all of these Fe2+ spectral features. Laboratory studies of mixed-mineral assemblages enable coexisting Fe2+ phases to be identified in remote-sensed reflectance spectra of regoliths. Thus, noritic rocks in the lunar highlands, troctolites in central peaks of impact craters such as Copernicus, and high-Ti and low-Ti mare basalts have been mapped on the Moon's surface by telescopic reflectance spectroscopy. The Venusian atmosphere prevents remote-sensed spectral measurements of its surface mineralogy, while atmospheric CO2 and ferric-bearing materials in the regolith on Mars interfere with pyroxene characterization in bright- and dark-region spectra. Reflectance spectral measurements of several meteorite types, including specimens from Antarctica, are consistent with a lunar highland origin for achondrite ALHA 81005 and a martian origin for shergottite EETA 79001, although source regions may not be outermost surfaces of the Moon and Mars. Correlations with asteroid reflectance spectra suggest that Vesta is the source of basaltic achondrites, while wide ranges of olivine/pyroxene ratios are inconsistent with an ordinary-chondrite surface composition of many asteroids. Visible-near-infrared spectrometers are destined for instrument payloads in future spacecraft missions to neighbouring solar system bodies.
Contributors
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- By Ghazi Al-Rawas, Vazken Andréassian, Tianqi Ao, Stacey A. Archfield, Berit Arheimer, András Bárdossy, Trent Biggs, Günter Blöschl, Theresa Blume, Marco Borga, Helge Bormann, Gianluca Botter, Tom Brown, Donald H. Burn, Sean K. Carey, Attilio Castellarin, Francis Chiew, François Colin, Paulin Coulibaly, Armand Crabit, Barry Croke, Siegfried Demuth, Qingyun Duan, Giuliano Di Baldassarre, Thomas Dunne, Ying Fan, Xing Fang, Boris Gartsman, Alexander Gelfan, Mikhail Georgievski, Nick van de Giesen, David C. Goodrich, Hoshin V. Gupta, Khaled Haddad, David M. Hannah, H. A. P. Hapuarachchi, Hege Hisdal, Kamila Hlavčová, Markus Hrachowitz, Denis A. Hughes, Günter Humer, Ruud Hurkmans, Vito Iacobellis, Elena Ilyichyova, Hiroshi Ishidaira, Graham Jewitt, Shaofeng Jia, Jeffrey R. Kennedy, Anthony S. Kiem, Robert Kirnbauer, Thomas R. Kjeldsen, Jürgen Komma, Leonid M. Korytny, Charles N. Kroll, George Kuczera, Gregor Laaha, Henny A. J. van Lanen, Hjalmar Laudon, Jens Liebe, Shijun Lin, Göran Lindström, Suxia Liu, Jun Magome, Danny G. Marks, Dominic Mazvimavi, Jeffrey J. McDonnell, Brian L. McGlynn, Kevin J. McGuire, Neil McIntyre, Thomas A. McMahon, Ralf Merz, Robert A. Metcalfe, Alberto Montanari, David Morris, Roger Moussa, Lakshman Nandagiri, Thomas Nester, Taha B. M. J. Ouarda, Ludovic Oudin, Juraj Parajka, Charles S. Pearson, Murray C. Peel, Charles Perrin, John W. Pomeroy, David A. Post, Ataur Rahman, Liliang Ren, Magdalena Rogger, Dan Rosbjerg, José Luis Salinas, Jos Samuel, Eric Sauquet, Hubert H. G. Savenije, Takahiro Sayama, John C. Schaake, Kevin Shook, Murugesu Sivapalan, Jon Olav Skøien, Chris Soulsby, Christopher Spence, R. ‘Sri’ Srikanthan, Tammo S. Steenhuis, Jan Szolgay, Yasuto Tachikawa, Kuniyoshi Takeuchi, Lena M. Tallaksen, Dörthe Tetzlaff, Sally E. Thompson, Elena Toth, Peter A. Troch, Remko Uijlenhoet, Carl L. Unkrich, Alberto Viglione, Neil R. Viney, Richard M. Vogel, Thorsten Wagener, M. Todd Walter, Guoqiang Wang, Markus Weiler, Rolf Weingartner, Erwin Weinmann, Hessel Winsemius, Ross A. Woods, Dawen Yang, Chihiro Yoshimura, Andy Young, Gordon Young, Erwin Zehe, Yongqiang Zhang, Maichun C. Zhou
- Edited by Günter Blöschl, Technische Universität Wien, Austria, Murugesu Sivapalan, University of Illinois, Urbana-Champaign, Thorsten Wagener, University of Bristol, Alberto Viglione, Technische Universität Wien, Austria, Hubert Savenije, Technische Universiteit Delft, The Netherlands
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- Runoff Prediction in Ungauged Basins
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- 05 April 2013
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- 18 April 2013, pp ix-xiv
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The Murchison Widefield Array: The Square Kilometre Array Precursor at Low Radio Frequencies
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- S. J. Tingay, R. Goeke, J. D. Bowman, D. Emrich, S. M. Ord, D. A. Mitchell, M. F. Morales, T. Booler, B. Crosse, R. B. Wayth, C. J. Lonsdale, S. Tremblay, D. Pallot, T. Colegate, A. Wicenec, N. Kudryavtseva, W. Arcus, D. Barnes, G. Bernardi, F. Briggs, S. Burns, J. D. Bunton, R. J. Cappallo, B. E. Corey, A. Deshpande, L. Desouza, B. M. Gaensler, L. J. Greenhill, P. J. Hall, B. J. Hazelton, D. Herne, J. N. Hewitt, M. Johnston-Hollitt, D. L. Kaplan, J. C. Kasper, B. B. Kincaid, R. Koenig, E. Kratzenberg, M. J. Lynch, B. Mckinley, S. R. Mcwhirter, E. Morgan, D. Oberoi, J. Pathikulangara, T. Prabu, R. A. Remillard, A. E. E. Rogers, A. Roshi, J. E. Salah, R. J. Sault, N. Udaya-Shankar, F. Schlagenhaufer, K. S. Srivani, J. Stevens, R. Subrahmanyan, M. Waterson, R. L. Webster, A. R. Whitney, A. Williams, C. L. Williams, J. S. B. Wyithe
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- Journal:
- Publications of the Astronomical Society of Australia / Volume 30 / 2013
- Published online by Cambridge University Press:
- 24 January 2013, e007
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The Murchison Widefield Array (MWA) is one of three Square Kilometre Array Precursor telescopes and is located at the Murchison Radio-astronomy Observatory in the Murchison Shire of the mid-west of Western Australia, a location chosen for its extremely low levels of radio frequency interference. The MWA operates at low radio frequencies, 80–300 MHz, with a processed bandwidth of 30.72 MHz for both linear polarisations, and consists of 128 aperture arrays (known as tiles) distributed over a ~3-km diameter area. Novel hybrid hardware/software correlation and a real-time imaging and calibration systems comprise the MWA signal processing backend. In this paper, the as-built MWA is described both at a system and sub-system level, the expected performance of the array is presented, and the science goals of the instrument are summarised.
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- By Rose Teteki Abbey, K. C. Abraham, David Tuesday Adamo, LeRoy H. Aden, Efrain Agosto, Victor Aguilan, Gillian T. W. Ahlgren, Charanjit Kaur AjitSingh, Dorothy B E A Akoto, Giuseppe Alberigo, Daniel E. Albrecht, Ruth Albrecht, Daniel O. Aleshire, Urs Altermatt, Anand Amaladass, Michael Amaladoss, James N. Amanze, Lesley G. Anderson, Thomas C. Anderson, Victor Anderson, Hope S. Antone, María Pilar Aquino, Paula Arai, Victorio Araya Guillén, S. Wesley Ariarajah, Ellen T. Armour, Brett Gregory Armstrong, Atsuhiro Asano, Naim Stifan Ateek, Mahmoud Ayoub, John Alembillah Azumah, Mercedes L. García Bachmann, Irena Backus, J. Wayne Baker, Mieke Bal, Lewis V. Baldwin, William Barbieri, António Barbosa da Silva, David Basinger, Bolaji Olukemi Bateye, Oswald Bayer, Daniel H. Bays, Rosalie Beck, Nancy Elizabeth Bedford, Guy-Thomas Bedouelle, Chorbishop Seely Beggiani, Wolfgang Behringer, Christopher M. Bellitto, Byard Bennett, Harold V. Bennett, Teresa Berger, Miguel A. Bernad, Henley Bernard, Alan E. Bernstein, Jon L. Berquist, Johannes Beutler, Ana María Bidegain, Matthew P. Binkewicz, Jennifer Bird, Joseph Blenkinsopp, Dmytro Bondarenko, Paulo Bonfatti, Riet en Pim Bons-Storm, Jessica A. Boon, Marcus J. Borg, Mark Bosco, Peter C. Bouteneff, François Bovon, William D. Bowman, Paul S. Boyer, David Brakke, Richard E. Brantley, Marcus Braybrooke, Ian Breward, Ênio José da Costa Brito, Jewel Spears Brooker, Johannes Brosseder, Nicholas Canfield Read Brown, Robert F. Brown, Pamela K. Brubaker, Walter Brueggemann, Bishop Colin O. Buchanan, Stanley M. Burgess, Amy Nelson Burnett, J. Patout Burns, David B. Burrell, David Buttrick, James P. Byrd, Lavinia Byrne, Gerado Caetano, Marcos Caldas, Alkiviadis Calivas, William J. Callahan, Salvatore Calomino, Euan K. Cameron, William S. Campbell, Marcelo Ayres Camurça, Daniel F. Caner, Paul E. Capetz, Carlos F. Cardoza-Orlandi, Patrick W. Carey, Barbara Carvill, Hal Cauthron, Subhadra Mitra Channa, Mark D. Chapman, James H. Charlesworth, Kenneth R. Chase, Chen Zemin, Luciano Chianeque, Philip Chia Phin Yin, Francisca H. Chimhanda, Daniel Chiquete, John T. Chirban, Soobin Choi, Robert Choquette, Mita Choudhury, Gerald Christianson, John Chryssavgis, Sejong Chun, Esther Chung-Kim, Charles M. A. Clark, Elizabeth A. Clark, Sathianathan Clarke, Fred Cloud, John B. Cobb, W. Owen Cole, John A Coleman, John J. Collins, Sylvia Collins-Mayo, Paul K. Conkin, Beth A. Conklin, Sean Connolly, Demetrios J. Constantelos, Michael A. Conway, Paula M. Cooey, Austin Cooper, Michael L. Cooper-White, Pamela Cooper-White, L. William Countryman, Sérgio Coutinho, Pamela Couture, Shannon Craigo-Snell, James L. Crenshaw, David Crowner, Humberto Horacio Cucchetti, Lawrence S. Cunningham, Elizabeth Mason Currier, Emmanuel Cutrone, Mary L. Daniel, David D. Daniels, Robert Darden, Rolf Darge, Isaiah Dau, Jeffry C. Davis, Jane Dawson, Valentin Dedji, John W. de Gruchy, Paul DeHart, Wendy J. Deichmann Edwards, Miguel A. De La Torre, George E. Demacopoulos, Thomas de Mayo, Leah DeVun, Beatriz de Vasconcellos Dias, Dennis C. Dickerson, John M. Dillon, Luis Miguel Donatello, Igor Dorfmann-Lazarev, Susanna Drake, Jonathan A. Draper, N. Dreher Martin, Otto Dreydoppel, Angelyn Dries, A. J. Droge, Francis X. D'Sa, Marilyn Dunn, Nicole Wilkinson Duran, Rifaat Ebied, Mark J. Edwards, William H. Edwards, Leonard H. Ehrlich, Nancy L. Eiesland, Martin Elbel, J. Harold Ellens, Stephen Ellingson, Marvin M. Ellison, Robert Ellsberg, Jean Bethke Elshtain, Eldon Jay Epp, Peter C. Erb, Tassilo Erhardt, Maria Erling, Noel Leo Erskine, Gillian R. Evans, Virginia Fabella, Michael A. Fahey, Edward Farley, Margaret A. Farley, Wendy Farley, Robert Fastiggi, Seena Fazel, Duncan S. Ferguson, Helwar Figueroa, Paul Corby Finney, Kyriaki Karidoyanes FitzGerald, Thomas E. FitzGerald, John R. Fitzmier, Marie Therese Flanagan, Sabina Flanagan, Claude Flipo, Ronald B. Flowers, Carole Fontaine, David Ford, Mary Ford, Stephanie A. Ford, Jim Forest, William Franke, Robert M. Franklin, Ruth Franzén, Edward H. Friedman, Samuel Frouisou, Lorelei F. Fuchs, Jojo M. Fung, Inger Furseth, Richard R. Gaillardetz, Brandon Gallaher, China Galland, Mark Galli, Ismael García, Tharscisse Gatwa, Jean-Marie Gaudeul, Luis María Gavilanes del Castillo, Pavel L. Gavrilyuk, Volney P. Gay, Metropolitan Athanasios Geevargis, Kondothra M. George, Mary Gerhart, Simon Gikandi, Maurice Gilbert, Michael J. Gillgannon, Verónica Giménez Beliveau, Terryl Givens, Beth Glazier-McDonald, Philip Gleason, Menghun Goh, Brian Golding, Bishop Hilario M. Gomez, Michelle A. Gonzalez, Donald K. Gorrell, Roy Gottfried, Tamara Grdzelidze, Joel B. Green, Niels Henrik Gregersen, Cristina Grenholm, Herbert Griffiths, Eric W. Gritsch, Erich S. Gruen, Christoffer H. Grundmann, Paul H. Gundani, Jon P. Gunnemann, Petre Guran, Vidar L. Haanes, Jeremiah M. Hackett, Getatchew Haile, Douglas John Hall, Nicholas Hammond, Daphne Hampson, Jehu J. Hanciles, Barry Hankins, Jennifer Haraguchi, Stanley S. Harakas, Anthony John Harding, Conrad L. Harkins, J. William Harmless, Marjory Harper, Amir Harrak, Joel F. Harrington, Mark W. Harris, Susan Ashbrook Harvey, Van A. Harvey, R. Chris Hassel, Jione Havea, Daniel Hawk, Diana L. Hayes, Leslie Hayes, Priscilla Hayner, S. Mark Heim, Simo Heininen, Richard P. Heitzenrater, Eila Helander, David Hempton, Scott H. Hendrix, Jan-Olav Henriksen, Gina Hens-Piazza, Carter Heyward, Nicholas J. Higham, David Hilliard, Norman A. Hjelm, Peter C. Hodgson, Arthur Holder, M. Jan Holton, Dwight N. Hopkins, Ronnie Po-chia Hsia, Po-Ho Huang, James Hudnut-Beumler, Jennifer S. Hughes, Leonard M. Hummel, Mary E. Hunt, Laennec Hurbon, Mark Hutchinson, Susan E. Hylen, Mary Beth Ingham, H. Larry Ingle, Dale T. Irvin, Jon Isaak, Paul John Isaak, Ada María Isasi-Díaz, Hans Raun Iversen, Margaret C. Jacob, Arthur James, Maria Jansdotter-Samuelsson, David Jasper, Werner G. Jeanrond, Renée Jeffery, David Lyle Jeffrey, Theodore W. Jennings, David H. Jensen, Robin Margaret Jensen, David Jobling, Dale A. Johnson, Elizabeth A. Johnson, Maxwell E. Johnson, Sarah Johnson, Mark D. Johnston, F. Stanley Jones, James William Jones, John R. Jones, Alissa Jones Nelson, Inge Jonsson, Jan Joosten, Elizabeth Judd, Mulambya Peggy Kabonde, Robert Kaggwa, Sylvester Kahakwa, Isaac Kalimi, Ogbu U. Kalu, Eunice Kamaara, Wayne C. Kannaday, Musimbi Kanyoro, Veli-Matti Kärkkäinen, Frank Kaufmann, Léon Nguapitshi Kayongo, Richard Kearney, Alice A. Keefe, Ralph Keen, Catherine Keller, Anthony J. Kelly, Karen Kennelly, Kathi Lynn Kern, Fergus Kerr, Edward Kessler, George Kilcourse, Heup Young Kim, Kim Sung-Hae, Kim Yong-Bock, Kim Yung Suk, Richard King, Thomas M. King, Robert M. Kingdon, Ross Kinsler, Hans G. Kippenberg, Cheryl A. Kirk-Duggan, Clifton Kirkpatrick, Leonid Kishkovsky, Nadieszda Kizenko, Jeffrey Klaiber, Hans-Josef Klauck, Sidney Knight, Samuel Kobia, Robert Kolb, Karla Ann Koll, Heikki Kotila, Donald Kraybill, Philip D. W. Krey, Yves Krumenacker, Jeffrey Kah-Jin Kuan, Simanga R. Kumalo, Peter Kuzmic, Simon Shui-Man Kwan, Kwok Pui-lan, André LaCocque, Stephen E. Lahey, John Tsz Pang Lai, Emiel Lamberts, Armando Lampe, Craig Lampe, Beverly J. Lanzetta, Eve LaPlante, Lizette Larson-Miller, Ariel Bybee Laughton, Leonard Lawlor, Bentley Layton, Robin A. Leaver, Karen Lebacqz, Archie Chi Chung Lee, Marilyn J. Legge, Hervé LeGrand, D. L. LeMahieu, Raymond Lemieux, Bill J. Leonard, Ellen M. Leonard, Outi Leppä, Jean Lesaulnier, Nantawan Boonprasat Lewis, Henrietta Leyser, Alexei Lidov, Bernard Lightman, Paul Chang-Ha Lim, Carter Lindberg, Mark R. Lindsay, James R. Linville, James C. Livingston, Ann Loades, David Loades, Jean-Claude Loba-Mkole, Lo Lung Kwong, Wati Longchar, Eleazar López, David W. Lotz, Andrew Louth, Robin W. Lovin, William Luis, Frank D. Macchia, Diarmaid N. J. MacCulloch, Kirk R. MacGregor, Marjory A. MacLean, Donald MacLeod, Tomas S. Maddela, Inge Mager, Laurenti Magesa, David G. Maillu, Fortunato Mallimaci, Philip Mamalakis, Kä Mana, Ukachukwu Chris Manus, Herbert Robinson Marbury, Reuel Norman Marigza, Jacqueline Mariña, Antti Marjanen, Luiz C. L. Marques, Madipoane Masenya (ngwan'a Mphahlele), Caleb J. D. Maskell, Steve Mason, Thomas Massaro, Fernando Matamoros Ponce, András Máté-Tóth, Odair Pedroso Mateus, Dinis Matsolo, Fumitaka Matsuoka, John D'Arcy May, Yelena Mazour-Matusevich, Theodore Mbazumutima, John S. McClure, Christian McConnell, Lee Martin McDonald, Gary B. McGee, Thomas McGowan, Alister E. McGrath, Richard J. McGregor, John A. McGuckin, Maud Burnett McInerney, Elsie Anne McKee, Mary B. McKinley, James F. McMillan, Ernan McMullin, Kathleen E. McVey, M. 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Yee, Viktor Yelensky, Yeo Khiok-Khng, Gustav K. K. Yeung, Angela Yiu, Amos Yong, Yong Ting Jin, You Bin, Youhanna Nessim Youssef, Eliana Yunes, Robert Michael Zaller, Valarie H. Ziegler, Barbara Brown Zikmund, Joyce Ann Zimmerman, Aurora Zlotnik, Zhuo Xinping
- Edited by Daniel Patte, Vanderbilt University, Tennessee
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- The Cambridge Dictionary of Christianity
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- 05 August 2012
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- 20 September 2010, pp xi-xliv
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P. Halbach, G. Friedrich & U. Von Stackelberg (eds) 1988. The Manganese Nodule Belt of the Pacific Ocean. Geological Environment, Nodule Formation, and Mining Aspects. x + 254 pp. Stuttgart: Ferdinand Enke Verlag. Price DM 186.00 (hard covers). ISBN 3 432 96381 5.
- Roger G. Burns
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- Geological Magazine / Volume 127 / Issue 1 / January 1990
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- 01 May 2009, p. 93
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2 - Isotopes of the transition elements
- Roger G. Burns, Massachusetts Institute of Technology
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- Mineralogical Applications of Crystal Field Theory
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- 23 November 2009
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- 16 September 1993, pp 462-463
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4 - Measurements of absorption spectra of minerals
- Roger G. Burns, Massachusetts Institute of Technology
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- Mineralogical Applications of Crystal Field Theory
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- 23 November 2009
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- 16 September 1993, pp 87-145
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Since ferrous iron usually colors minerals green, and ferric iron yellow or brown, it may seem rather remarkable that the presence of both together should give rise to a blue color, as in the case of vivianite. – – Other instances may perhaps be discovered, should this subject ever be investigated as it deserves to be.
E. T. Wherry, Amer. Mineral, 3, 161 (1918)Introduction
In order to apply crystal field theory to geologic processes involving transition metal ions, it is necessary to have crystal chemical information and thermodynamic data for these cations in mineral structures. In 2.8, it was noted that the principal method for obtaining crystal field splittings, and hence stabilization energies of the cations, is from measurements of absorption spectra of transition metal compounds at wavelengths in the visible and near-infrared regions. The origins of such absorption bands in crystal field spectra were discussed in chapter 3. The focus of this chapter is on measurements of absorption spectra of minerals, with some applications to fundamental crystal chemical problems.
When minerals occur as large, gem-sized crystals, it is comparatively easy to obtain absorption spectra by passing light through natural crystal faces or polished slabs of the mineral. However, most rock-forming minerals are present in assemblages of very small crystals intimately associated with one another, leading to technical problems for measuring spectra of minerals in situ. In addition, several of the transition elements occur in only trace amounts in common minerals, making spectral features of individual cations difficult to resolve, especially in the presence of more abundant elements such as iron, titanium and manganese which also absorb radiation in the visible to nearinfrared region.
References
- Roger G. Burns, Massachusetts Institute of Technology
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- Mineralogical Applications of Crystal Field Theory
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- 23 November 2009
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- 16 September 1993, pp 478-522
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5 - Group theory nomenclature for crystal field states
- Roger G. Burns, Massachusetts Institute of Technology
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- Mineralogical Applications of Crystal Field Theory
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- 23 November 2009
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- 16 September 1993, pp 467-467
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6 - Crystal chemistry of transition metal-bearing minerals
- Roger G. Burns, Massachusetts Institute of Technology
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- Mineralogical Applications of Crystal Field Theory
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- 23 November 2009
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- 16 September 1993, pp 240-271
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Summary
A great deal has been written about the crystal-field model for first-row transition metal cations in the distorted octahedra of olivines. – – Its predictions are useful for – – rationalizing the intra- and inter-crystalline cation partitioning.
G. E. Brown Jr, Rev. Mineral, 5 (2nd edn), 333 (1982)Introduction
The crystal chemistry of many transition metal compounds, including several minerals, display unusual periodic features which can be elegantly explained by crystal field theory. These features relate to the sizes of cations, distortions of coordination sites and distributions of transition elements within the crystal structures. This chapter discusses interatomic distances in transition metal-bearing minerals, origins and consequences of distortions of cation coordination sites, and factors influencing site occupancies and cation ordering of transition metals in oxide and silicate structures, which include crystal field stabilization energies
Interatomic distances in transition metal compounds
One property of a transition metal ion that is particularly sensitive to crystal field interactions is the ionic radius and its influence on interatomic distances in a crystal structure. Within a row of elements in the periodic table in which cations possess completely filled or efficiently screened inner orbitals, there should be a decrease of interatomic distances with increasing atomic number for cations possessing the same valence. The ionic radii of trivalent cations of the lanthanide series for example, plotted in fig. 6.1, show a relatively smooth contraction from lanthanum to lutecium.
Mineralogical Applications of Crystal Field Theory
- 2nd edition
- Roger G. Burns
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- 23 November 2009
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- 16 September 1993
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The second edition of this classic book provides an updated look at crystal field theory - one of the simplest models of chemical bonding - and its applications. Crystal field theory provides a link between the visible region spectra and thermodynamic properties of numerous rock-forming minerals and gems that contain the elements iron, titanium, vanadium, chromium, manganese, cobalt, nickel or copper. These elements are major constituents of terrestrial planets and significantly influence their geochemical and geophysical properties. A unique perspective of the second edition is that it highlights the properties of minerals that make them compounds of interest to solid-state chemists and physicists as well as to all earth and planetary scientists. This book will be useful as a textbook for advanced students as well as a valuable reference work for all research workers interested in this subject.
Preface to the second edition
- Roger G. Burns, Massachusetts Institute of Technology
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Summary
When the first edition of Mineralogical Applications of Crystal Field Theory was written during 1968–9, it broke new ground by describing results and suggesting applications of the limited spectroscopic and crystal chemical data then available for transition metal-bearing minerals. The data were derived mainly from visible to near-infrared spectral measurements, together with newly available Mössbauer-effect studies of iron minerals, made principally at ambient temperatures and pressures. The book stimulated considerable interest among subsequent mineral spectroscopists who have developed new and improved methods to study minerals and synthetic analogues under a variety of experimental conditions, including in situ measurements made at elevated temperatures and pressures. As a result, the quantity of spectral and crystal chemical data has increased appreciably and may now be applied to a diversity of current new problems involving transition elements in the earth and planetary sciences.
The second edition now attempts to review the vast data-base of visible to near-infrared spectroscopic measurements of minerals containing cations of the first-series transition elements that has appeared during the past 20 years. Several newer applications of the spectral and crystal chemical data are described, including interpretations of remote-sensed reflectance spectra used to identify transition metal-bearing minerals on surfaces of planets. This topic alone warrants the inclusion of a new chapter in the second edition. Many of the classical applications of crystal field theory outlined in the first edition are retained, and each of the original 10 chapters is expanded to accommodate fresh interpretations and new applications of crystal field theory to transition metal geochemistry.
11 - Covalent bonding of the transition elements
- Roger G. Burns, Massachusetts Institute of Technology
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Summary
Theories of chemical bonding – – fall into one of two categories: those which are too good to be true and those which are too true to be good.
F. A. Cotton, J. Chem. Educ., 41, 475 (1964).Introduction
In earlier chapters, allusions were made to the effects of covalent bonding. For example, covalent interactions were invoked to account for the intensification of absorption bands in crystal field spectra when transition metal ions occupy tetrahedral sites (3.7.1); patterns of cation ordering for some transition metal ions in silicate crystal structures imply that covalency influences the intracrystalline (or intersite) partitioning of these cations (6.8.4); and, the apparent failure of the Goldschmidt Rules to accurately predict the fractionation of transition elements during magmatic crystallization was attributed to covalent bonding characteristics of these cations (8.3.2).
A fundamental assumption underlying the crystal field model of chemical bonding is that ligands may be treated as point negative charges with no overlap of metal and ligand orbitals. Thus, 3d electrons are assumed to remain entirely on the transition metal ion with no delocalization into ligand orbitals. This situation is never realized, even in ionic structures such as periclase (MgO) and forsterite (Mg2SiO4), let alone bunsenite (NiO), liebenbergite (Ni2SiO4) or fayalite (Fe2SiO4), in which metal–oxygen bonds have some degree of covalent character and electrons in metal orbitals participate in the bonding. Some of the fundamental features of crystal field theory are contrary to expectation or are impossible to derive using the point charge model (Cotton, 1964).
7 - Thermodynamic properties influenced by crystal field energies
- Roger G. Burns, Massachusetts Institute of Technology
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Summary
These observations (non-linear heats of hydration) suggest the following hypothesis: In the absence of crystal-field effects the thermodynamic properties – – would evolve steadily along the transition series.
L. E. Orgel, Journ. Chem. Soc., p. 4756 (1952).Introduction
One of the most successful applications of crystal field theory to transition metal chemistry, and the one that heralded the re-discovery of the theory by Orgel in 1952, has been the rationalization of observed thermodynamic properties of transition metal ions. Examples include explanations of trends in heats of hydration and lattice energies of transition metal compounds. These and other thermodynamic properties which are influenced by crystal field stabilization energies, including ideal solid-solution behaviour and distribution coefficients of transition metals between coexisting phases, are described in this chapter.
Influence of CFSE on thermodynamic data
Graphical correlations
Crystal field stabilization energies derived spectroscopically from absorption bands in the visible to near-infrared region, including the crystal field spectral measurements of minerals described in chapter 5, are enthalpy terms and, as such, might be expected to contribute to bulk properties such as lattice energies and solvation energies of transition metal compounds. If cations were spherically symmetrical and no preferential filling of 3d orbitals occurred, a given thermodynamic quantity would be expected to display smooth periodic variation in a series of transition metal compounds as a result of contraction of the cations.
6 - Correlations between the Schöenflies and Hermann–Mauguin symbols
- Roger G. Burns, Massachusetts Institute of Technology
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3 - Ionic radii of transition metals and related cations
- Roger G. Burns, Massachusetts Institute of Technology
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9 - Mantle geochemistry of the transition elements: optical spectra at elevated temperatures and pressures
- Roger G. Burns, Massachusetts Institute of Technology
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It is embarassing that the pressure experiments show the dependence of Δ upon the distance R between the metal and the ligand to be fairly close to that given by the point charge model.
S. Sugano & S. Oshnishi, in Material Science of the Earth's Interior. (I. Sunagawa, ed., Terra Scientific Publ. Co., Tokyo, 1984), p. 174Introduction
Considerable interest centres on the Mantle constituting, as it does, more than half of the Earth by volume and by weight. Attention has been focussed on several problems, including the chemical composition, mineralogy, phase transitions and element partitioning in the Mantle, and the geophysical properties of seismicity, heat transfer by radiation, electrical conductivity and magnetism in the Earth. Many of these properties of the Earth's interior are influenced by the electronic structures of transition metal ions in Mantle minerals at elevated temperatures and pressures. Such effects are amenable to interpretation by crystal field theory based on optical spectral data for minerals measured at elevated temperatures and pressures.
In the Mantle, temperatures range up to several thousands of degrees Kelvin and pressures may exceed 100 GPa in the deep interior, attaining 136 GPa at the Core–Mantle boundary. In the past two decades, the optical spectra of several minerals and synthetic analogues have been measured at high pressures and elevated temperatures simulating conditions in the interior of the Earth. The results of many of these high P and T spectral measurements are reviewed in this chapter and applications of the spectral data are described to transition metal-bearing Mantle minerals.
5 - Crystal field spectra of transition metal ions in minerals
- Roger G. Burns, Massachusetts Institute of Technology
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The end products of the analysis (measurement and interpretation of mineral absorption spectra by crystal field theory) are some parameters that can be correlated with structural properties.
K. L. Keester & W. B. White, Proc. 5th IMA Meeting (Cambridge, 1966), p. 22 (1968)Introduction
In the previous chapter it was shown how measurements of polarized absorption spectra in the visible to near-infrared region can provide information on such crystal chemical problems as oxidation states of transition metal ions, coordination site symmetries and distortions, cation ordering and the origins of colour and pleochroism of minerals. Much attention was focused in chapter 4 on energies of intervalence charge transfer transitions appearing in electronic absorption spectra of mixed-valence minerals.
Perhaps a more fundamental application of crystal field spectral measurements, and the one that heralded the re-discovery of crystal field theory by Orgel in 1952, is the evaluation of thermodynamic data for transition metal ions in minerals. Energy separations between the 3d orbital energy levels may be deduced from the positions of crystal field bands in an optical spectrum, making it potentially possible to estimate relative crystal field stabilization energies (CFSE's) of the cations in each coordination site of a mineral structure. These data, once obtained, form the basis for discussions of thermodynamic properties of minerals and interpretations of transition metal geochemistry described in later chapters.
1 - Abundance data for the transition elements
- Roger G. Burns, Massachusetts Institute of Technology
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8 - Chemical and physical constants, units and conversion factors
- Roger G. Burns, Massachusetts Institute of Technology
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- 16 September 1993, pp 475-477
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