Mineral Surface Chemistry Group

Carrick M. Eggleston

An important part of geochemistry is the study of how rocks and minerals at the Earth's surface interact with our chemical environment. Surfaces are fundamental to understanding how rocks and minerals communicate chemically with their surroundings, and to predicting the response of natural systems to environmental problems. Work in our group focuses on the fundamental chemistry of mineral surfaces as it pertains to geo- and environmental chemistry. Recently, our research has (1) taken a turn toward the mechanics of biological electron transfer between bacteria and minerals, and (2) started to concentrate effort on photocatalysts that might be used in solar hydrogen or methanol generation (we are working mainly on hematite photocatalysts whose behavior also has geochemical implications).

Publications

Current projects include:

1) Redox-linked conformation change: electron transfer from bacterial proteins to minerals

Dissimilatory iron-reducing bacteria couple the oxidation of organic matter (food) to the reduction of ferric iron.  Because Fe(III) is generally insoluble at mid-range pH, this respiratory feat involves electron transfer from the organism to a solid mineral surface.  Because it has been shown that c-type cytochromes are central to this process, we have engaged in the study of the interaction of specific proteins with iron oxide electrode surfaces using electrochemical and microscopic/spectroscopic techniques.  We are studying proteins from Shewanella oneidensis MR-1, Acidiphilium cryptum, and Geobacter sulfurreducens.  In addition to isolated proteins, we are studying the electrochemical behavior of living microbial populations in contact with iron oxide electrodes.  This is a collaboration with Prof. Patricia J.S. Colberg (UW Department of Zoology and Physiology) and Prof. Tim Magnuson (Idaho State University), and is funded by the NSF through 2007.

A project that builds on #1, and that will quantify such things as protein adsorption density, protein physical density, redox potentials, surface packing, and optical absorption properties, is funded by the U.S. Department of Energy through 2009.

Plots of cytochrome adsorption as f(time) and f(pH)AFM images of bacteria
Left: Adsorption of the outer-membrane decaheme cytochrome OmcA as a function of time and of pH and ionic strength.  The image at right shows not only bacteria on a surface, but also "nanowires" as described by Dr. Yuri Gorby at PNNL.


2) Biogeochemistry Grand Challenge: Metal-Reducing Bacteria

In a project similar to #1, in collaboration with a range of outstanding scientists from Pacific Northwest National Laboratory and elsewhere, we are engaged in a study of proteins isolated and purified from the outer membrane of Shewanella oneidensis MR-1.  These are generally multiheme proteins with fascinating electrochemical behavior.  This project is funded by the Pacific Northwest National Laboratory through 2007.

OmcA electrochemistryplot of voltammograms

The voltammograms at left show a prominent reduction wave at about -300 mV vs. Ag/AgCl for a solution containing the outer-membane cytochrome OmcA (hematite electrode).  The plot at right shows currents from an experiment using whole cell suspensions of MR-1 through an anaerobic-aerobic cycle.

3) Waveguide Scanning Photocurrent Microscopy (WaSPM).

This project is funded by the U.S. Department of Energy through 2009, and has the purpose of developing a novel imaging technique capable of molecular-scale resolution and based on optical tunneling coupled to photocurrent detection using a photocatalytic probe tip.

Anisotropic photocurren (hematite)

The plot above shows anisotropic photocurrents for hematite (dark currents are given in red and black, photocurrents are given as blue and pink).


NOTE:  We are seeking a qualified postdoctoral research scientist to participate in projects 3 and 1!!  Please inquire by emailing Carrick M. Eggleston, carrick@uwyo.edu

4) Solar Fuels and Iron Oxide Photocatalyst Properties

The Eggleston research group is also initiating work on photocatalysis for generation of fuels, including hydrogen and methanol fuels, using sunlight and water or carbonate-saturated water.  Proposals are underway in this subject area, which is new for the group and results from a sabbatical leave during the 2005-2006 academic year associated with the Laboratory for Photonic and Interfaces (LPI)  under Prof. Michael  Graetzel at the Ecole Polytechnique Federale de Lausanne (EPFL).  As part of this, we are also initiating a systematic study of reductive dissolution of hematite under electrochemical control using well-characterized hematite electrodes.  This has not been systematically studied previously, despite its global geochemical importance.  This project is the result of another collaboration with Prof. Jean-Jacques Ehrhardt at the Laboratory for the Physical Chemistry and Microbiology of the Environment (CNRS) in Nancy, France.