Andy at TEM.jpg

CONTACT

University of Oklahoma
School of Geology and Geophysics 
100 East Boyd St. Rm 834
amadden@ou.edu
(405) 325-5327 phone
(405) 325-3140 fax

 

goethite1scale web.jpg

Transmission Electron Microscope image of goethite demonstrating multidomanic nature of particles

gypsum

Atomic force microscope image of gypsum

HFO

Transmission Electron Microscope image of hydrous ferric oxide

thin section

Atomic force microscope image of polished rock thin section

Links

 

 

 

 

 

 

 

 

 

 

 

 

Assistant Professor OU logo
School of Geology and Geophysics, University of Oklahoma

Postdoctoral Research Associate, 2005-2007, Oak Ridge National Laboratory
Ph.D. (geochemistry), 2005, Virginia Tech
B.S. (geology), 2000, Michigan State University

ENVIRONMENTAL BIOGEOCHEMISTRY

My research interests and expertise lie in the exploration of fundamental low-temperature biogeochemical processes at mineral surfaces influencing the distribution of metals and radionuclides in the environment.   Methods include the application of nanoscience, nanotechnology, and microbiology to environmental water chemistry.  Additional interests include the relevance of fundamental processes at the mineral-water-bacterial interface to water quality and remediation projects. 

I am co-director of the Physical and Environmental Geochemistry Laboratory with Dr. Megan Elwood Madden.

For examples of research facilites and projects, please visit the websites for the laboratories.

PUBLICATIONS

Elwood Madden ME, Madden AS, Rimstidt JD (2009) How long was Meridiani Planum wet? Applying a jarosite stopwatch to constrain the duration of diagenesis, Geology 37(7) 635-638. Link

Grady JR and Madden AS (in press) Integrating the sciences to investigate groundwater pollution, Science Activities.

Bose S, Lower BH, Gorby YA, Kennedy DW, McCrady DE, Madden AS, Hochella MF Jr., (2009) Bioreduction of hematite nanoparticles by the dissimilatory iron reducing bacterium Shewanella oneidensis MR-1, Geochimica et Cosmochimica Acta. Link

Madden AS, Palumbo AV, Ravel B, Vishnivetskaya TA,Phelps TJ, Schadt CS, Brandt CC, (2009) Donor-dependent extent of uranium reduction for bioremediation of contaminated sediment microcosms, Journal of Environmental Quality. Link

Bank TL, Kukkadapu RK, Madden AS, Ginder-Vogel MA, Baldwin ME, Jardine PM (2008) Effects of sterilization on the physico-chemical properties of natural sediments from the oak ridge reservation, Chemical Geology 251:1-7.   Link

Chernyshova IV, Hochella MF, Madden AS (2007) Size-dependent structural transformations of hematite nanoparticles. 1. Phase transition, Physical Chemistry Chemical Physics 9, 1736-1750. Link

Madden AS, Knefel AC, Grady JR, Glasson GE, Hochella MF, Jr., Eriksson SC, Bank TL, Cecil K, Green A, Hurst D, Norris M, Schreiber ME (2007) Nano2Earth: Incorporating cutting-edge research into secondary education through scientist-educator partnerships, Journal of Geoscience Education 55(5), 402-412. Link

Madden AS, Smith AC, Balkwill DL, Fagan LA, Phelps TJ (2007) Microbial uranium immobilization independent of nitrate reduction, Environmental Microbiology 9(9), 2321–2330. Link

Velbel MA, McGuire JT, and Madden AS (2007) Scanning electron microscopy of garnet from southern Michigan soils: Etching rates and inheritance of pre-glacial and pre-pedogenic grain-surface textures, Developments in Sedimentology, 58, 413-432. Link

Madden AS, Hochella MF, Jr., and Luxton TD (2006) Insights for size-dependent reactivity of hematite nanomineral surfaces through Cu2+ sorption, Geochimica et Cosmochimica Acta 70(16) 4095-4014. Link

Foresti E, Hochella MF, Jr., Lesci IG, Madden AS, Roveri N, and Xu H (2005) Morphological and chemical-physical characterization of Fe doped synthetic chrysotile nano-crystals, Advanced Functional Materials 15(6): 1009-1016. Link

Hochella MF, Jr., and Madden, AS (2005) Earth’s nano-compartment for toxic metals, Elements 1(4) 199-203. Download

Madden AS, and Hochella MF, Jr. (2005) A test of geochemical reactivity as a function of mineral size: Manganese oxidation promoted by hematite nanoparticles, Geochimica et Cosmochimica Acta 69(2) 389-398. Link

TEACHING  

Fall 2007 GEOL 3154 Environmental Geology (with lab)
Spring 2008 GEOL 1114 Physical Geology for Scientists and Engineers
Fall 2008 GEOL 1104 The Dynamic Earth
GEOL 6970 Minerals and the Environment
Spring 2009 GEOL 3154 Environmental Geology (with lab)

EXAMPLES OF RESEARCH ACCOMPLISHMENTS

Nanogeoscience

Imagine you are holding a crystal of hematite (iron oxide) in your hand, 1 cm on each side.  You would like to know something about it, so you measure all of its properties that you can think of: it’s melting temperature, crystal structure, its color, its behavior in the presence of magnetic fields, and its chemical reactivity.  Now imagine that the hematite is only 1 mm on a side.  When you repeat the measurements, you are likely to get the same answers.  Repeat the measurements again on a hematite crystal with 1 micron (1/1000  mm) length sides – once again, you get many of the same answers!  This is the size of typical bacteria.  Once the length scales of the crystal sides begins to shrink below 100 nanometers (1 nm = 10^-9 m or 10^-6 mm), some of those properties may start to change as a function of the crystal size.  In fact, as the size of the crystal decreases towards 1 nm, more properties change at an increasingly rapid rate.  The fundamental measurements that we know about this material, ‘hematite’, are no longer fixed- they’re a function of the particle size!

That is nanoscience. In order to study things at the nanoscale, or manipulate them to do something we want, special tools are needed.  Or maybe the size-dependence of a material can be used for something beneficial.  In the Earth and environmental sciences, vast amounts of materials are found in the length scale of 1-100 nm that have novel properties because of their small size. 

How does the geochemical reactivity of Earth and environmental materials change in the nanoscale size range? Over what length scales does the size-dependence occur? Size dependent studies of nanomineral reactivity include metal sorption, surface-mediated redox reactions, photochemical reduction, formation, stability, and colloidal behavior.

Exploring the reactivity of nanominerals: redox reactions

Exploring the reactivity of nanominerals: metal sorption

Defining reactive surface area of nanoparticles. The surface area of mineral particles can be measured or defined in a variety of ways, including by gas adsorption (such as in the BET method) or geometric models.  The surface area is a key parameter in many geochemical experiments and models.  Which is the most appropriate surface area to use, and does “one size fit all” for every type of geochemical reaction? How accessible are spaces between aggregates to ions in solution, including potential contaminants? For example, in a collaborative study, our nanoscale characterization of goethite has shown that a different surface area is appropriate for phosphate and proton sorption due to the presence of nanoporosity not accessible to P. Also, we have demonstrated a 'cross-over' size delineating appropriate size ranges for geometric vs. BET surface areas for hematite nanoparticles.

Hematite nanominerals

 

 

Transmission Electron Microscopy is used to image materials of a few to tens of nanometers in diameter, such as these hematite nanominerals.

 

 

 

Nanogeoscience education

Nano2Earth

We are currently working with the national Center for the Environmental Implications of NanoTechnology to complete development and distribution of our curriculum, "Nano2Earth: Introducing nanotechnology through investigations of groundwater." for secondary school courses.

Environmental / interfacial biogeochemistry

Reactions at the interfaces between minerals, water, and bacteria biogeochemistry often determine the distribution, reactivity, and fate of chemical elements.  These interfacial biogeochemical processes lead to the redistribution of metals in soils, surface water, and groundwater.  Relatively high concentrations of metals in water threaten the sustainability of our water supplies.  These contaminants include natural forms resulting from higher concentrations of metals in regional source rocks, those associated with mining and industrial impacted waters, and those related to the nuclear power / weapons complex.  In addition to the fundamental science of interfacial biogeochemistry, this research area include the coupling of biological processes and mineral surface processes to enhance the effectiveness of remediation.

Uranium bioremediation

Nitrate-indifferent uranium reduction: Uranium immobilization in contaminated ground water and sediment may be achieved by the addition of electron donors to stimulate microbial activity.  Microbial communities in the subsurface have the capacity to immobilize several metal contaminants, but are limited in activity by the lack of suitable electron donor substrates for energy yield and growth.  When stimulated with added electron donors, oxidized, soluble metals such as U(VI) are transformed to reduced, insoluble forms through various metabolic processes.  Previous studies have shown that while uranium bioremediation through electron donor is possible, several significant challenges exist.  For example, electron donors shown to rapidly decrease aqueous uranium concentrations do not necessarily reduce a majority of the sediment uranium, such that sorbed or mineral U(VI) forms may continue to release uranium to groundwater after cessation of electron donor addition.  In fact, such rebound of groundwater uranium concentrations has been observed in several field and laboratory experiments.   At many uranium processing and handling facilities, including sites in the US Department of Energy (DOE) complex, high levels of nitrate are present as co-contamination with uranium in groundwater. The daunting prospect of complete nitrate removal prior to the reduction of uranium provides a strong incentive to explore bioremediation strategies that allow for uranium bioreduction and stabilization in the presence
of nitrate. Typical in situ strategies involving the stimulation of metal-reducing bacteria are hindered by low-pH environments and require that the persistent nitrate must first and continuously be removed or transformed prior to uranium being a preferred electron acceptor. This work investigated the possibility of stimulating nitrate-indifferent, pH-tolerant microorganisms to achieve bioreduction of U(VI) despite nitrate persistence. Enrichments from U-contaminated sediments demonstrated nearly complete reduction of uranium with very little loss of nitrate from pH 5.7–6.2 using methanol or glycerol as a carbon source. Bacterial 16S rRNA genes were amplified from uranium-reducing enrichments (pH 5.7–6.2) and sequenced. Phylogenetic analyses classified the clone sequences into four distinct clusters. Data from sequencing and terminal-restriction fragment length polymorphism (T-RFLP) profiles indicated that the majority of the microorganisms stimulated by these enrichment conditions consisted of low G+C Gram-positive bacteria most closely related to Clostridium and Clostridium-like organisms. This research demonstrates that the stimulation of a natural microbial community to immobilize U through bioreduction is possible without the removal of nitrate. PROJECT LEADER: Tommy Phelps.

Electron donor-dependence of uranium reduction: The specific electron donor used to stimulate uranium bioreduction has great significance for the resultant rate and extent of reduction.  In completed microcosm experiments, it has been shown that pyruvate addition results in an increase in aqueous U contentrations, ethanol addition results in rapid reduction of aqueous U(VI) but only ~43% total sediment U reduction.  On the other hand, at near-neutral pH methanol slowly reduces aqueous uranium but leads to much greater (~93% in our microcosm experiments) total sediment U reduction in the same time period.  Also, at low pH, methanol can stimulate nitrate-indifferent uranium reduction, avoiding an initial lag period where nitrate is first removed. Madden et al. (JEQ) report that the particular electron donor chosen affects not only the rate of U(VI) reduction to insoluble U(IV) but also the total extent of reduction.  Microcosm experiments demonstrated equivalent rapid uranium reduction when amended with ethanol or glucose.  In contrast, reduction was delayed by several days when microcosms were amended with methanol.  Spectroscopic analyses of uranium oxidation state in stimulated microcosm sediment slurries demonstrated almost complete uranium reduction when methanol was the donor, as compared with less than half reduced using ethanol or glucose.  These results suggest that the use of donors such as methanol which are not as readily and rapidly coupled to microbial metal reduction may lead to increased stability of the subsurface towards uranium immobilization. PROJECT LEADER: Tony Palumbo.

uranium phosphate and goethitePhosphate-based uranium precipitation on mineral surfaces. In-situ remediation of metals and radionuclides in the subsurface depends on the coupling of biogeochemical and microbiological processes. Fundamental science at the mineral-water-bacteria interface can guide strategies to sequester contaminants. We are currently investigating the role in mineral surface structure on the immobilization of uranium through phosphate addition.

 

Right: Atomic Force Microscopy image of uranium phosphate precipitated with goethite.

 

Additional projects include collaboration with Tommy Phelps (Biosciences Division at Oak Ridge National Laboratory) to study the incorporation of uranium into magnetite during biologically-mediated precipitation.      

RECENT PRESENTATIONS

Madden AS (2009) Crossover size for best hematite nanoparticle surface area measurement, American Chemical Society 237th Annual Meeting, Salt Lake City, UT.

Chernyshova IV, Fang X, Ponnurangam S, Somasundaran P, Madden AS, Hochella MF Jr. (2008) Adsorption modes of natural carbonate indicate that the surface basicity of hematite nanoparticles increases with a decrease of particle size. American Chemical Society236th Annual Meeting, Philadelphia, PA.

Elwood Madden ME, Guess JR, Madden AS, Rimstidt JDR (2008) Jarosite lifetimes on Earth and Mars from dissolution rates. Goldschmidt Conference, Vancouver BC, Canada.

Elwood Madden ME, Guess JR, Madden AS, Rimstidt JDR (2008) Estimating Duration of Diagenesis at Meridiani Planum from Jarosite Dissolution Rate, Geological Society of America Annual Meeting, Houston TX.

Heard G, Pannalal J, Elmore RD, Whittington RA, Elliott WC, Engel M, Zechmeister M, Aufill M, and Madden AS (2008) The Origin of the Magnetic Susceptibility Signal in the Woodford Shale, Southern Oklahoma, Geological Society of America Annual Meeting, Houston TX.

Madden AS (2008) Nanogeoscience and AFM at OU-Norman.  Oklahoma Microscopy Society Annual Meeting.

Madden AS and Hochella MF (2008) Significance of size-dependent reactivity for hematite particle size distributions. Goldschmidt Conference, Vancouver BC, Canada.

Madden AS, Vishnivetskaya TA, Palumbo AV, Brandt CC, Pfiffner SM, Fagan LA, Smith AC, Balkwill DL, Phelps TJ (2008) Electron donor strategies for bioremediation of uranium-contaminated sediments.  University of Oklahoma Department of Botany and Microbiology.

Pannalal J, Heard G, Elmore RD, Whittington RA, Elliott WC, Engel M, Zechmeister M, Aufill M, and Madden AS (2008) Magnetic Susceptibility and Late Paleozoic Secondary Magnetizations in the Woodford Shale, Oklahoma: Role of Diagenesis, Oklahoma Gas Shales Conference.

Nanoscience, bioremediation, and metals in the environment (2007) University of Oklahoma, School of Geology and Geophysics.

DiFurio S, Pfiffner SM, Fagan LA, McNeilly MS, Madden AS, Brandt CC, Palumbo AV (2007) Effects of carbon source addition and sediment source on uranium reduction and microbial diversity in sediment microcosms. American Society for Microbiology.

Madden AS, Smith AC, Balkwill DL, Phelps TJ (2007) Bioremediation Approaches for Nirtate-Independent Uranium Reduction.  DOE Environmental Remediation Sciences Program Principal Investigators meeting, Lansdowne, VA.

Palumbo AV, Schadt CW, Brandt CC, McNeilly MS, Madden AS, Fagan LA, Mills HJ, Akob DM, DiFurio S, Pfiffner SM, Kostka JE (2007) An Integrated Assessment of Geochemical and Community Structure Determinants of Metal Reduction Rates in Subsurface Sediments. DOE Environmental Remediation Sciences Program Principal Investigators meeting, Lansdowne, VA.

Vishnivetskaya TA, Palumbo AV, Brandt CC, Pfiffner SM, Fagan LA, Madden AS, McNeilly MS, Kostka JE (2007) Variability in community changes in response to carbon amendment for U reduction. American Society for Microbiology.

Madden AS, Smith AC, Balkwill DL, Fagan LA, Phelps TJ (2006) Bioremediation Approaches for Sustained Uranium Immobilization Independent of Nitrate Reduction.  DOE Environmental Remediation Sciences Program Principal Investigators meeting, Airlie, VA.

Palumbo AV, Brandt CC, Pfiffner SM, Fagan LA, Madden AS, Schryver JC, McNeilly MS, Phelps TJ, Schadt CW, Tarver JR, Kostka JE (2006) An Integrated Assessment of Geochemical and Community Structure Determinants of Metal Reduction Rates in Subsurface Sediments. DOE Environmental Remediation Sciences Program Principal Investigators meeting, Airlie, VA.

Palumbo AV, Brandt CC, Pfiffner SM, Fagan LA, Madden AS, Schryver JC, McNeilly MS, Phelps TJ, Schadt CW, Tarver JR, Kostka JE (2006) Methanol Stimulated Uranium Reduction: Does Community Heterogeneity Matter? AGU, San Francisco.

Smith AC, Madden AS, Balkwill DL, Phelps TJ (2006) Microbial Community Responses to Nitrate-Indifferent Uranium Bioreduction. AGU, San Francisco.

Hochella MF Jr., Madden AS, Bose S, and Wigginton NS (2006) The Role of Nanoscience in the Field of Environmental Mineralogy. AGU Joint Congress, Baltimore MD.

Smith AC, Madden AS, Balkwill DL, Fagan LA, Phelps TJ (2006) Bioremediation approaches for sustained uranium immobilization independent of nitrate reduction. American Society for Microbiology.

Palumbo AV, Brandt CC, Pfiffner SM, Fagan LA, Madden AS, Schryver JC, McNeilly MS, Phelps TJ, Schadt CW, Tarver JR, Kostka JE (2006) Reduction processes and community structure in remediation of uranium. American Chemical Society, Atlanta.

Hochella MF, Madden AS, Glasson GE, Eriksson SC (2005) Keynote address: Nano2Earth: Transforming Cutting-Edge Nanoscience into a Curriculum for Biogeochemistry and Earth Systems Science Teachers.  Teaching Geochemistry in the 21st Century, University of Idaho, Moscow, ID

McGuire JT, Velbel MA, Brandt DS, Madden AS (2005) An extreme environment episodic fossilization of microorganisms; geochemical controls and implications for paleoastrobiology (in North American paleontology convention, Dinosaurs to dinoflagellates; programme and abstracts,
PaleoBios 25(2, Suppl.):82-83.

Madden AS and Hochella MF, Jr. (2005) Cu2+ as a probe for nanomineral surface chemistry. American Geophysical Union, San Francisco.

Yeary LW, Phelps TJ, Love LJ, Moon J, Rondinone AJ, Rawn CJ, Thompson JR, Madden AS, Elwood Madden ME (2005) Magnetic characteristics of metal-doped magnetite nanoparticles produced by Thermoanaerobacter Ethanolicus. American Geophysical Union, San Francisco.

Madden AS and Hochella MF, Jr. (2004) Photochemical reduction of iron oxide nanoparticles as a function of mineral size.  Geological Society of America Annual Meeting. Foresti E, Hochella MF, Jr., Lesci IG, Madden AS, Roveri N, and Xu H (2004) Morphological and chemical-physical characterization of Fe doped synthetic chrysotile nano-crystals. GSA Annual Meeting.

Hochella MF, Jr., Madden AS, and Moore JN (2004) The importance of nanoparticles and their unusual properties in sediments and soils from heavy-metal contaminated sites.  GSA Annual Meeting.

Madden AS and Hochella MF, Jr. (2004) A test of geochemical reactivity as a function of mineral size: Manganese oxidation promoted by hematite nanoparticles.  American Chemical Society national meeting, Anaheim, CA.

Madden AS, Green A, and Norris M (2004) Microbes, Minerals, and Water: From Contamination to Clean-up.  Virginia Tech 2004 Biotechnology Educator’s Conference.

Eriksson SC, Madden AS, Glasson GE, Hochella MF, Jr., Schreiber MS (2004) Nano2Earth: Introducing nanotechnology through investigations of groundwater pollution, for secondary biology, chemistry, and Earth and environmental science teachers. Geological Society of America Annual Meeting (poster).

Hochella MF, Jr., Madden AS, Moore JN, Kasama T, Putnis A, and Putnis CV (2004) An example of the environmental importance of nanoparticles: The formation and consequences of nanoparticulate Fe and Mn hydrous oxides from a massive acid mine drainage system.  Goldschmidt conference, Denmark.

Tadanier CJ, Madden AS, and Eick MJ (2004) Ordered water in surface complexation modeling.  Goldschmidt conference, Denmark.

Velbel MA, McGuire JT, Madden AS, Brandt DS, and Long DT (2004) Episodic fossilization of microorganisms on an annual timescale in an anthropogenically modified natural environment: geochemical controls and implications for astrobiology. Lunar and Planetary Science Conference XXXV, abstract #1346. Lunar and Planetary Science Institute, Houston (CD-ROM).

Glasson GE, Eriksson SC, Madden AS, Grady J, Green A, Hurst D (2003) Nanoscience and nanotechnology.  Virginia Association of Science Teachers Fall Conference, Portsmouth, VA.

Eriksson SC, Glasson GE, Swami N, Porter R, and Madden AS (2003) Nanotechnology and Nanoscience.  National Consortium for Specialized Secondary Schools of Mathematics, Science & Technology annual conference, Roanoke, VA.

Eriksson SC, Glasson GE, and Madden AS (2002) Nanoscience and Secondary Science Curriculum Development.  Virginia Association of Science Teachers 2002 Conference, Richmond, VA.

Hochella MF, Jr., Tadanier CJ, Lower SK, Lower BH, Kendall TA, Cail TL, and Madden AS (2003) Mineral-fluid interfaces and interactions: From molecular to local, regional, and global-scale processes.  Goldschmidt conference, Japan.

Madden AS and Velbel MA (2000) Reaction-path modeling of kaolinite formation during silicate weathering in a southern Blue Ridge saprolitic regolith on high-grade metamorphic rocks at the Coweeta Hydrologic Laboratory, North Carolina.  Clay Minerals Society Annual Meeting.

Madden AS, Velbel MA, McGuire JT, Reynolds LA, Brandt DS, Haack SK, Long DT, Hyndman DW, and Klug MJ (2000) Episodic fossilization of microbes on an annual timescale in a contaminated aquifer.  Geological Society of America Annual Meeting.

Velbel MA, McGuire JT, and Madden AS (2000) Scanning electron microscopy of garnet from southern Michigan soils: Etching rates and inheritance of pre-glacial and pre-pedogenic grain-surface textures. North Central Geological Society of America Meeting.


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