Haydn Murray Chair of Applied Clay Mineralogy
- Postdoctoral fellow, 1977-1980, Harvard University
- Ph.D., 1977, Pennsylvania State University
- B.S., 1974, Furman University, High honors
I concentrate on the application of crystal chemical and crystal structural fundamentals to geological, materials, and environmental problems. Much of my recent work has focused on understanding the structures, properties, and origins of fine-grained minerals, such as clay minerals and natural zeolites, using a multidisciplinary approach. For example, in a recent study of kaolinite origin, I focused on an analysis of the degree of crystalline order present within samples using computer simulation of powder diffraction patterns, showing that kaolinite order varies greatly as a function of particle size (some samples showing the best order in the finest fractions). I later combined these studies with trace-element (REE) analyses as a function of size fraction to gain a more complete picture of kaolinite genesis (and also showing that the trace-element content of natural kaolins is attributable mostly to their trace mineral content). My recent studies of the surface properties of smectites were similar, including diffraction, spectroscopic, and surface chemistry analyses. Although fundamental in nature, these surface property studies are of great importance in understanding many applied aspects of smectite behavior, from their ability to swell osmotically, to uses in landfills, to predicting new uses of surface-modified smectites as organic adsorbents. Other applied mineralogical studies include my work on the behavior of fluorine in brick raw materials (clay minerals), the measurement of trace erionite in natural zeolite products, and a variety of studies on the importance of clay and zeolite minerals in radioactive waste applications.
My research often involves powder diffraction methods, including the Rietveld method, a powerful technique that facilitates extraction of a tremendous amount of quantitative information from diffraction patterns of solids. I have clarified the structures of a number of important fine-grained minerals using a combination of X-ray and neutron powder diffraction methods with spectroscopic techniques. For example, I recently elucidated the nature of the interaction of hydrazine, an environmental pollutant, with the mineral kaolinite using diffraction and spectroscopic methods. I have also been a pioneer in the development of the Rietveld quantitative analysis method. This method provides quantitative mineralogic information on fine-grained rocks, with precision comparable to that obtained in X-ray fluorescence analyses. Although I have concentrated on X-ray powder diffraction methods, I also routinely use neutron powder diffraction methods in my research. Neutron diffraction is uniquely suited to studies of hydrous minerals such as clays and zeolites. Unlike X-ray diffraction that is insensitive to H atoms, neutrons are strongly diffracted by H atoms, allowing determination of quantitative information on the conformation of H, particularly OH, in minerals. This is quite important because OH groups and water molecules determine much about a mineral’s behavior. For example, it is the conformation of interlayer H atoms in kaolinite (and in clay minerals in general) that determines the interlayer stacking and how strongly the layers are held together. I participate in the neutron diffraction community, and I understand that the IU Cyclotron Facility is proposing to build a university-based pulsed neutron source at IU. Such a facility would be quite valuable as both a research tool for the study of minerals and as an educational tool, to illustrate the multidisciplinary nature of materials studies.
I am also particularly interested in the study of minerals under controlled–T, –P(H2O) conditions. Such experiments routinely provide new insights into the structures and behavior of materials that analyses under room conditions do not provide. These experiments are particularly important in understanding and predicting applications of minerals under real-world conditions because many minerals are used under conditions quite distinct from typical laboratory conditions of T and
P(H2O). An example of these studies is my research on the thermal and sorptive behavior of minerals at the potential high-level radioactive waste repository at Yucca Mountain, Nevada. This work included X-ray diffraction under non-ambient conditions and emphasized the effects of long-term heating of a variety of minerals, including clays and zeolites. I recently combined this research with thermodynamic modeling to provide insights into the coupled effects of temperature and water vapor pressure on mineral stability.
My experience in experimental studies of minerals under non-ambient conditions has recently been expanded to cover studies of potential martian hydrous minerals. This research initially concentrated on whether or not hydrous zeolites and clay minerals could exist on the martian surface in a hydrated state, thereby partially accounting for the water that has been observed heterogeneously distributed on the present-day martian surface. More recently, I have expanded this research to studies of hydrated salt minerals, including magnesium and iron sulfates. Both of these have either been implicated based on spectroscopic or chemical data or have actually been observed on the martian surface. The magnesium sulfates form a fantastic array of hydrated phases, some of which are undoubtedly stable in a hydrated state on the present-day martian surface. The iron sulfates also exist in a wide variety of hydration states and many different structures and our recent data show that they have very low thermal stabilities. Ongoing studies will assess whether or not they might be stable on the martian surface.
- G171, Environmental Geology
- G221, Mineralogy
- G427, X-ray Mineralogy
- G601, Clay Mineralogy
My teaching philosophy combines traditional geology and mineralogy education with my experiences in the more-applied world of Los Alamos National Laboratory, where I worked for 23 years prior to coming to Indiana University. Thus, I feel it is important to provide students not only with the chemical and mineralogical foundations to geological systems, but also to give an appreciation for and experience with real-world problems involving their use. I am excited by both basic and advanced courses in mineralogy, with a focus on fine-grained minerals such as clays and zeolites and on rock-forming minerals. I also find applied courses such as environmental mineralogy, industrial mineralogy, and extraterrestrial mineralogy to be ideal avenues for putting the fundamental chemical and mineralogical foundations to work. In all of my courses I try to consider what I found to be important throughout my career at Los Alamos and, in this way, my teaching is tempered by my real-world (if one can call Los Alamos National Laboratory “real world”) experiences. I will periodically teach advanced courses related to my fields of interest, including X-ray crystallography, powder diffraction, spectroscopy, and thermal analysis.
Recent Research Projects
Development of a miniaturized X-ray diffraction/X-ray fluorescence instrument for planetary exploration (CHEMIN).
Studies of the stability of possible martian hydrous minerals under simulated Mars surface conditions.
Quantification of the surface properties of clay minerals and implications for their use in environmental applications.
Use of X-ray powder diffraction in quantifying mineral abundances.
Application of the Rietveld method to determining quantitative crystal structural information from fine-grained minerals using X-ray powder diffraction data.
Graduate Student Projects
Origin of Terra Rossa from southern Indiana
Mineralogy of Pleistocene sediments from Nantucket Island, Massachusetts
Dehydration/rehydration-induced structural phase transitions in natrolite.
Surface properties of silicate clay minerals and their modification by steam treatment
Structural and gravimetric evaluation of the structures of cation-exchanged smectites
Behavior of Mars analog hydrated sulfate minerals under simulated martian conditions.
Effects of compositional variations on crystal structures minerals in the jarosite-alunite series.
Mineralogy of low-temperature evaporite deposits in Antarctica: Natural analogs to martian evaporites?
Isotopic and organic geochemistry of Georgia kaolin deposits
Undergraduate Projects and Opportunities
There are many opportunities for research in the X-ray diffraction laboratory, studying the structures of minerals and how they change with temperature and environment. Several students are presently working me on the stability of hydrous minerals under simulated Mars atmospheric conditions. The results of student research projects are often presented at national meetings, usually in the form of a poster presentation.
Funding opportunities include the IU Undergraduate Research and Creative Activity Partnership and there are many opportunities for summer research here and at other universities.
F. Poulet, D. W. Beaty, J-P Bibring, D. Bish, J. L. Bishop, E. Noe Dobrea, J. F. Mustard, S. Petit, and L. H. Roach (2009) Key science questions and key investigations from the first international conference on Martian phyllosilicates. Astrobiology, 9, 257-267.
H. Ma, D. L. Bish, H-W. Wang, and S. Chipera (2009) Determination of the crystal structure of sanderite, MgSO4•2H2O, by X-ray powder diffraction and charge flipping. American Mineralogist, 94, in press, (letter).
E. M. Hausrath, A. Treiman, E. Vicenzi, D. L. Bish, D. Blake, P. Sarrazin, T. Hoehler, I. Midtkandl, A. Steele, and S. L. Brantley, (2008) Short- and long-term olivine weathering in Svalbard, and implications for Mars. Astrobiology, 8, 1079-1092.
H-W. Wang and D. L. Bish (2008) A PH2O-dependent structural phase transition in the zeolite natrolite. American Mineralogist, 93, 1191-1194 (letter).
G. M. Bowers, D. L. Bish, and R. J. Kirkpatrick (2008) H2O and Cation Structure and Dynamics in Expandable Clays: 2H and 39K NMR Investigations of Hectorite. J. Physical Chem., 112, 6430-6438.
C. T. Johnston, J. E. Kogel, D. L. Bish, T. Kogure, and H. H. Murray (2008) Low-temperature FTIR study of kaolin-group minerals. Clays and Clay Minerals, 56, 470-485.
G. M. Bowers, D. L. Bish, and R. J. Kirkpatrick (2008) Cation exchange at the mineral-water interface: H3O+/K+ competition at the surface of nano-muscovite. Langmuir, 24, 10240-10244.
J. Jänchen, R. V. Morris, D. L. Bish, M. Janssen, and U. Hellwig (2008) The H2O and CO2 adsorption properties of phyllosilicate-free palagonitic dust and smectites under martian environmental conditions. Geophys. Res. Letters, 10.1016/j.icarus.2008.12.006.
E. A. Cloutis, M. A. Craig, J. F. Mustard, R. V. Kruzelecky, W. R. Jamroz, A. Scott, D. L. Bish, F. Poulet, J.-P. Bibring, P. L. King (2007) Stability of hydrated minerals on Mars. Geophys. Res. Lett., 34, L20202, doi:10.1029/2007GL031267.
J. E. Post, D. L. Bish, and P. J. Heaney (2007) Synchrotron powder X-ray diffraction study of the structure and dehydration behavior of sepiolite. American Mineralogist, 92, 91-97.
T. Tokano and D. L. Bish (2005) Hydration state and abundance of zeolites on Mars and the water cycle. J. Geophys. Res., 110, E12S08, doi:10.1029/2005JE002410.
J. Jänchen, D. L. Bish, D. T.F. Möhlmann, and H. Stach (2005) Investigation of the water sorption properties of Mars-relevant micro- and mesoporous minerals. Icarus, 180, 353-358.
D. T. Vaniman, pdf], S. J. Chipera, C. I. Fialips, J. W. Carey, and W. Feldman (2004) Formation and Transformation of Magnesium Sulfate Salts on Mars. Nature, 431, 663-665. [
W. C. Feldman, T. H. Prettyman, S. Maurice, J. J. Plaut, pdf], D. T. Vaniman, M. T. Mellon, A. E. Metzger, S. W. Squyres, S. Karunatillake, W. V. Boynton, R. C. Elphic, H. O. Funsten, D. J. Lawrence, and R. L. Tokar (2003) Global distribution of near-surface hydrogen on Mars. J. Geophys. Res., 109, E09006, 13 pp. [
pdf], J. W. Carey, D. T. Vaniman, S. J. Chipera (2003) Stability of hydrous minerals on the martian surface. Icarus, 164, 96-103. [
Awards and Honors
Vice-president, Mineralogical Society of America, 2009-2010
Participating Scientist, Mars Phoenix Lander, 2008-
George Brown Lecture Award of the Clay Minerals Group, Mineralogical Society of Great Britain, 2007
Ralph Grim Lecturer, University of Illinois, March, 2007
President, International Association for the Study of Clays (AIPEA), 2005-2009
Brindley Lecture Award, The Clay Minerals Society, 2002.
Co-recipient of a 1999 R&D100 Award for "CHEMIN: A Miniaturized X-ray Diffraction and X-ray Fluorescence Instrument"
Jackson Clay Scientist Award, The Clay Minerals Society, 1995
Fellow, Mineralogical Society of America, 1990-present
Graduate Studies Committee, Indiana University Department of Geological Sciences
Memeber, Policy Committee, Indiana University Department of Geological Sciences
Member, Undergraduate Honors Advisor, Indiana University Department of Geological Sciences
President, International Natural Zeolite Association, 2002-2006
President, International Committee on Natural Zeolites, 2002-2006
Member of Council, Mineralogical Society of America, 1999-2002
President, The Clay Minerals Society, 1998-1999
Vice-president, The Clay Minerals Society, 1997-1998
Board Member, International Committee on Natural Zeolites, 1997-present
Mineralogical Society of America National University Lecturer, 1997-1998
Associate Editor, Zeitschrift für Kristallographie, 1996-1999
Associate Editor, Clays and Clay Minerals, 1993-1996, 2002-2003
Associate Editor, American Mineralogist, 1987-1991, 2002
The mineralogy facilities at IU consist of several laboratories including an X-ray diffraction laboratory, a thermal analysis laboratory, and a clay mineral and sample preparation laboratory.
The X-ray diffraction laboratory is equipped with two automated Bruker D8 Advance diffractometers. One instrument, with a SolX energy-dispersive detector, is equipped with an ambient-temperature environmental stage capable of controlling gas composition or humidity (from 0 to 95%). The other instrument, with a Vantec position-sensitive detector, is equipped with an Anton-Parr TTK450 heating/cooling stage. This instrument allows examination of specimens under conditions of controlled temperature (from 77 to 723K) and atmosphere (vacuum, selected gas atmospheres, controlled relative humidity, 0-95%). A full complement of crystallographic and data analysis software is available, including several Rietveld refinement packages (GSAS, DBW, Topas), quantitative analysis routines (Fullpat, Diffrac), profile refinement packages (Topas), and structure solution (Topas-A).
The thermal analysis laboratory is equipped with several programmable furnaces for mineral equilibria studies up to 1000°C. Teflon-lined Parr vessels can be used for hydrothermal studies up to 250°C. A TA Instruments Simultaneous TGA/DSC instrument can be used to study the weight-loss behavior of solids and can simultaneously measure the enthalpic effects associated with thermal reactions. A new IGASorp-CT instrument was operational in 2007 and allows measurement of water-vapor adsorption isotherms from 57°C to 350°C, using partial pressures of water up to at least 500 mbar.
Our laboratory also includes a Quantachrome NOVA 1000 BET surface area analyzer and an ATS Reologica Viscoanalyser, capable of a wide variety of rheological measurements on suspensions.
The sample preparation laboratory contains a full complement of sample preparation equipment, including a Retsch Micro-Rapid mill with agate grinding set, a variety of mortars and pestles, a ultrasonic probe and bath and a Waring blender for sample disaggregation, a Sorvall high-speed centrifuge, and a variety of specialized specimen holders.