Academic Appointments


Administrative Appointments


  • Terry Huffington Professor of Earth Science, Stanford University (2011 - Present)
  • Senior Fellow (by courtesy) Woods Institute for the Environment, Stanford University (2008 - Present)
  • Professor Environmental Earth System Science, Stanford University (2007 - Present)
  • Affiliate Faculty, IPER, Stanford University (2005 - Present)
  • Associate Professor of Geological & Environmental Sciences, Stanford University (2003 - 2007)
  • Assistant Professor of Geological & Environmental Sciences, Stanford University (1999 - 2002)
  • Affiliate Faculty, Stanford Synchrotron Radiation Laboratory (1999 - Present)
  • Associate Professor, Soil Science Division, University of Idaho (1998 - 1999)
  • Adjunct Professor, Chemistry Department, University of Idaho (1997 - 1999)
  • Affiliate Staff Scientist, Pacific Northwest Laboratory (1994 - Present)
  • Assistant Professor Soil Science Division, University of Idaho (1993 - 1998)
  • Graduate Research Fellow, University of Delaware (1990 - 1992)

Honors & Awards


  • Fellow, Soil Science Society of America (2009)
  • Presidential, Citation for Outstanding Achievement, University of Delaware (2005)
  • Outstanding Teaching Award, School of Earth Science, Stanford University (2005)
  • Fellow, Stanford University (2004-2006)
  • Marion L. and Chrystie M. Jackson Soil Science Award for Outstanding Contributions in Soil Chemistry, Soil Science Society of America (2001)
  • Terman Fellow, Stanford University (1999)
  • Emil Truog Award for Outstanding Dissertation in Soil Science, Soil Science Society of America (1993)
  • Theodore Wolf Prize for Outstanding Dissertation in the Physical and Life Sciences, University of Delaware (1993)
  • Outstanding Graduate Student Award, SSSA-Northeast Division, Soil Science Society of America (1992)
  • Scholar, Soil & Water Conservation Service Scholarship (1988)

Boards, Advisory Committees, Professional Organizations


  • Soil Chemistry Division Chair Elect, Soil Science Society of America (2011 - 2012)
  • Member, Conference Committee, Soil Science Society of America (2011 - 2013)
  • Symposium Organizer (with Shawn Benner and Ruben Kretzchmar), “Biogeochemical Processes within Floodplain and Deltaic Sediments”, Goldschmidt conference, Prague, CZ, Goldschmidt conference (2011 - 2011)
  • Advisory board member, Delaware Environmental Institute (2010 - Present)
  • Co-Chair, Wood Institute for the Environment EVP Selection Committee, Stanford University (2009 - 2010)
  • Member, U.S. National Committee for Soil Science (2009 - Present)
  • Organizer, AGU Chapman Conference on Arsenic in Groundwater of Southern Asia, Siem Reap, Cambodia, American Geophysical Union (2009 - 2009)
  • Symposium Organizer (with Ruben Kretzchmar), “Biogeochemistry at Redox Interfaces”, Goldschmidt Conference, Davos, Switzerland, Goldschmidt Conference (2009 - 2009)
  • Invited Presentation: Stanford Ethics Society Seminar Series, Stanford University (2009 - 2009)
  • Invited Presentation: Stanford Synchrotron Radiation Laboratory Seminar Series, Stanford Linear Accelerator Laboratory (2009 - 2009)
  • Invited Presentation: ETH Seminar Series, Zurich, ETH Zürich (German: Eidgenössische Technische Hochschule Zürich) (2009 - 2009)
  • Associate Editor, Vadose Zone Journal (2009 - Present)
  • Committee on Undergraduate Standards and Policy, Stanford University (2008 - Present)
  • SIGF Selection Committee, Stanford University (2008 - Present)
  • Facility Representative for the Environmental Spectroscopy and Biogeochemistry Program, and member of the Advisory Council, Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory (2007 - 2009)
  • University Committee on Environmental Health and Safety, Stanford University (2007 - Present)
  • Chair, EESS, Stanford University (2007 - Present)
  • Faculty Director, Environmental Measurements Facility, Stanford University (2006 - Present)
  • Associate Chair, GES, Stanford University (2006 - 2007)
  • ERE Faculty Selection Committee, Stanford University (2006 - 2007)
  • Session Organizer, Influence of Coupled Biological, Chemical, and Physical Processes on Contaminant Fate and Transport, Program Investigator meeting, DOE Environmental Remediation Science (2006 - 2006)
  • Invited Lecture, "Biogeochemical Processes Governing the Fate of Chromium and Uranium within Soils and Waters”, Stanford Environmental Engineering and Science Seminar Series, Stanford University (2006 - 2006)
  • Invited Lecture: “Heterogeneity in Biogeochemical Processes Impacting Contaminant Fate and Transport, Annual Meeting, Department of Energy Environmental Remediation Science Program (2006 - 2006)
  • Invited Lecture: “Pathways of Ferric (Hydr)oxide Reductive Transformation and Impacts on Contaminant Transport”, Telluride Workshop: Iron Redox Chemistry at Environmentally Relevant Surfaces, Telluride Workshop (2006 - 2006)
  • Invited Lecture: Biogeochemical Processes Governing the Cycling of Arsenic in Surface and Subsurface Environments”, National Meeting, American Chemical Society (2006 - 2006)
  • Invited Lecture: “The Largest Mass Poisoning in History: Arsenic in Drinking Water”, Pinhead Institute’s Public Lecture, Telluride, CO, Pinhead Institute (2006 - 2006)
  • Invited lecture: “Processes Governing the Transport of Arsenic: Contrasts Between the Mekong and Ganges-Brahmaputra Deltas”, Columbia University Earth Science Forum (2006 - 2006)
  • Invited Lecture: “Dependency of Electron Transfer Rates on Changing and Localized Solid Phase Chemistry”, Biogeochemical Grand Challenge, Pacific Northwest National Laboratory (2006 - 2006)
  • Invited lecture: Processes Controlling the Toxicity and Transport of Chromium and Arsenic in Groundwater, Advanced Photon Source Scientific Advisory Board Meeting (2005 - 2005)
  • EEES Advisory Committee, Stanford University (2005 - Present)
  • GES Undergraduate Environmental Earth Science Curriculum Committee, Stanford University (2005 - 2006)
  • UPS Endowment Review Committee, Stanford University (2005 - Present)
  • SES Undergraduate Environmental Science Program Committee, Stanford University (2005 - Present)
  • Wood Institute for the Environment Research Committee, Stanford University (2005 - Present)
  • Invited lecture:Processes Controlling the Cycling of Arsenic in Soils and Sediments, Bath, UK, British Mineralogy Society (2005 - 2005)
  • Stanford Institute for the Environment Research Committee, Stanford University (2005 - 2005)
  • Invited lecture: Solid-Phase Species (Associations) of Arsenic in Bengal Basin Sediments, Symposium on Arsenic in Bangladesh, MIT (2005 - 2005)
  • Invited lecture:What Stands Between Environmental Toxins and Drinking Water? Stanford Graduate Student Lecture Series, Stanford Unversity (2005 - 2005)
  • Invited lecture:Soils Earth Systems 10 Lecture; Biogeochemical processes controlling the cycling of arsenic, EMSI seminar, Stanford University (2005 - 2005)
  • Invited lecture: Processes Governing the Largest Mass Poisoning in History: Arsenic in Drinking Water of Asia, University of Delaware (2005 - 2005)
  • Invited lectureIntegrated Process Controls on Elemental Cycling within the Critical Zone. National Science Foundation Workshop on Frontiers in Exploration of the Critical Zone, University of Delaware (2005 - 2005)
  • Invited lecture: Gaining a Molecular-Level Understanding of Processes Governing the Fate and Transport of Ions/Chemical within Soils Frontiers in Soil Science Research, Washington, DC, National Academy of Sciences (2005 - 2005)
  • nvited lecture: Biotransformation Rates of Iron Governing Chromium and Uranium Transport (Winter), National Meeting, San Francisco, CA, American Geophysical Union (2005 - 2005)
  • Participant and speaker for workshop on Frontiers in Soil Science Research, National Academy of Sciences (2005 - 2005)
  • Participant in Workshop on Frontiers in Exploration of the Critical Zone, National Science Foundation (2005 - 2005)
  • Invited lecture: The Greatest Mass Poisoning in History: Processes of Arsenic Liberation to Drinking Water in Asia. Earth Science Seminar Series, University of California, Santa Cruz (2005 - 2005)
  • Guest Editor, special issue on Controls on Arsenic Transport in Near-Surface Aquatic Systems, Chemical Geology (2005 - 2006)
  • GES Admissions Committee Chair, Stanford University (2004 - 2005)
  • Symposium Organizer, Mechanisms of Electron Transfer at the Mineral-Water Interface, National Meeting, Seattle, Soil Science Society of America (2004 - 2004)
  • SES Graduate Academic Programs Committee, Stanford University (2004 - 2005)
  • Earth Science Council Member, Stanford University (2004 - Present)
  • NSF Workshop participant on Preparing for an Academic Career in Geosciences, University of Minnesota, 2004, National Science Foundation (2004 - 2004)
  • Organizing member of ISSM/ISBE Symposia, ISSM/ISBE (2004 - 2005)
  • Invited lecture: Mechanisms of arsenic cycling: Current conditions in Bangladesh and emerging situations throughout Asia. Geology Club Seminar, California Institute of Technology (2004 - 2004)
  • Invited lecture: Processes controlling arsenic cycling in surface and subsurface environments, Purdue University (2004 - 2004)
  • Invited lecture: Mechanisms biomineralization of Fe(II) sequestration following dissimilatory iron reduction of structurally diverse Fe(III) (hydr)oxides. Water-Rock Interactions, Saratoga, NY, Saratoga, NY (2004 - 2004)
  • Invited lecture: Soils of Jasper Ridge, Docent Lecture Series, JRBP, Stanford University (2004 - 2004)
  • Invited lecture: What Stands Between Environmental Toxins and Drinking Water? Graduate Student Lecture, Stanford University (2004 - 2004)
  • GES Admissions Committee, Chair, Stanford University (2003 - 2004)
  • GES Long-range Planning Committee, Stanford University (2003 - 2003)
  • NSF Workshop participant on Preparing for an Academic Career in Geosciences, Stanford University, National Science Foundation (2003 - 2003)
  • Sexual Harassment Officer, School of Earth Sciences, Stanford University (2003 - 2009)
  • Symposium Organizer, Arsenic Dynamics within Soils and Sediments, National Meeting, Denver, Soil Science Society of America (2003 - 2003)
  • Review Panel Member for DOE-EPSCoR program, Department of Energy (2003 - 2003)
  • Symposium Organizer, Synchrotron Techniques in Environmental Microbiology and Biogeochemistry, , Annual Meeting, Stanford, CA, Stanford Synchrotron Radiation Laboratory (2003 - 2003)
  • Invited Lecture Process controlling the release of arsenic in surface and subsurface environments. USGS Seminar Series, Menlo Park, CA, U.S. Geological Survey (2003 - 2003)
  • Invited Lecture: Processes governing the fate of arsenic within the surface and near-surface environment. Biogeochemistry Seminar Series, Stanford University (2003 - 2003)
  • Invited Lecture: Arsenic cycling within surface and subsurface environments: The addiction to iron. Thermal Biology Institute Seminar Series, Bozeman, MT, Montana State University (2003 - 2003)
  • Invited Lecture: Microbially mediate reductive transformations of ferric oxides: Impacts on Cr and U dynamics, Scripps Institute of Oceanography (2003 - 2003)
  • Invited Lecture: Reductive biotransformations within soils and sediments: Controlling factors in the mobility of heavy metals and radionuclides, Oregon Graduate Institute (2003 - 2003)
  • Invited Lecture: Cycling and global threats of arsenic, National Meeting, Denver, CO, Soil Science Society of America (2003 - 2003)
  • Invited lecture: Arsenic cycling within surface and subsurface environments: Impact of iron mineralogy. National Meeting, New York, NY, American Chemical Society (2003 - 2003)
  • Invited Lecture: Speciation and desorption mechanisms of arsenic within Bangladesh sediments, National Meetings, Denver, CO, Soil Science Society of America (2003 - 2003)
  • Invited lecture: Mechanisms of arsenic cycling, School of Earth Sciences, Stanford University (2003 - 2003)
  • Invited Lecture: Biogeochemistry of metal reduction, Grand Challenge Seminar, Pacific Northwest National Laboratory (2003 - 2003)
  • Invited Lecture: Iron transformations under biological reducing conditions, Geological Sciences Seminar, UC Berkeley (2002 - 2002)
  • Invited Lecture: Arsenic dynamics within reducing soil/sediment environments, Environmental Science: Water. Plymouth, NH, Gordon Conference (2002 - 2002)
  • Invited Lecture: Biogenic evolution of microscale heterogeneity: Impact on contaminant dynamics Goldschmidt Conference, Davos, Switzerland, Goldschmidt Conference (2002 - 2002)
  • Invited Lecture: Uranium retention by biogenic magnetite Goldschmidt Conference, Davos, Switzerland, Goldschmidt Conference (2002 - 2002)
  • Invited Lecture:Sustained Microbial Metabolism and Contaminant Sequestration Upon Reductive Biomineralization of Ferric Hydroxides, San Francisco, CA, American Geophysical Union. (2002 - 2002)
  • Invited Lecture:Modeling the reactive transport and biomineralization of ferrihydrite reductive dissolution, Orlando, FL, American Chemical Society (2002 - 2002)
  • Invited Lecture:Mechanisms of Fe biomineralization induced by dissimilatory iron reduction, Orlando, FL, American Chemical Society (2002 - 2002)
  • Invited Lecture: Impact of solid-phase alterations on reduction pathways of chromate, Orlando, FL, American Chemical Society (2002 - 2002)
  • Goldschmidt Planning Committee, Geochemical Society (2002 - 2005)
  • Invited Lecture:Unique Physical and Chemical Properties of Soils. Stanford Community Farm, Stanford University (2001 - 2001)
  • Member, Search Committee, Geomicrobiology, Stanford University (2001 - 2002)
  • Earth Systems Advisory Council, Stanford University (2001 - Present)
  • Member, GES Long-range Planning Committee, Stanford University (2001 - 2004)
  • Invited Lecture Reduction of chromium in surface and subsurface environments: Contributions of biological and abiological processes. Goldschmidt Conference, Hot Springs, VA, Goldschmidt Conference (2001 - 2001)
  • Invited Lecture Reductive dissolution and biomineralization of iron oxides under dynamic flow conditions. Goldschmidt Conference, Hot Springs, VA, Goldschmidt Conference (2001 - 2001)
  • Invited Lecture Element-specific microtomographic imaging of metal distribution (and speciationNULL) in contaminated systems, Chicago, IL, American Chemical Society (2001 - 2001)
  • Member, Undergraduate Program Committee for GES, Stanford University (2001 - 2002)
  • Invited Lecture Defining the speciation and chemical dynamics of contaminants within the vadose zone, San Francisco, CA, American Geophysical Union National Meetings (2001 - 2001)
  • Invited Lecture: Speciating trace elements within natural environments: Impacts on bioavailability, International Conference on the Bioavailability of Trace Elements (2001 - 2001)
  • Soil Science Advisory Council, Soil Science Department, San Luis Obispo, California Polytechnic State University (2000 - Present)
  • Committee member, Defining Contaminant Bioavailability in Soils and Sediments, National Research Council (2000 - 2002)
  • Invited Lectures: Environmental influential reactions and speciation of sulfur within soils and waters, SSRL Workshop on Chemistry of Sulfur in the Environment, Stanford, CA, Stanford Synchrotron Radiation Lightsource (2000 - 2000)
  • Review Panel Member for National Research Competitive Grants Program in Soil and Soil Biology, USDA (1999 - 1999)
  • Review Panel Member for DoD's Strategic Environmental Research and Development Program (SERDP), Department of Defense (1999 - 1999)
  • Selection committee member for Outstanding Researcher in Soil Science, Soil Science Society of America (1999 - 2002)
  • Invited Lecture: Competing biological and geochemical processes in metal and radionuclide reduction, DOE workshop Combined Chemical and Microbiological Approaches to Remediating Metal and Radionuclide Contaminants, Reston, VA, DOE (1999 - 1999)
  • Review Panel Member for PNNL's Laboratory Directed Research and Development Program, Pacific Northwest National Laboratory (1998 - 1998)
  • Associate Editor, Journal of Environmental Quality (1998 - 2000)
  • Invited Lecture: Trace element cycling within the Coeur d'Alene River system. Department of Geology Seminar Series, University of Idaho, Moscow (1998 - 1998)
  • Invited Lecture: Metal ion structures within soil environments. Department of Chemistry Seminar Series, University of Idaho (1998 - 1998)
  • Invited Lecture: Fundamental aspects and applications of x-ray absorption spectroscopy in clay and soil science. Clay Mineral Society Workshop on Applications of Synchrotron Radiation in Clay Science, Ottawa, Canada, Clay Mineral Society Workshop (1997 - 1997)
  • Committee member for Soil Science Society of America Emil Truog Outstanding Graduate Student Award, Soil Science Society of America (1996 - 1998)
  • Selection committee member for American Society of Agronomy Environmental Quality Research Award Committee (A447), American Society of Agronomy (1996 - 1999)
  • Member of NCR-174, Soil Scientists for Synchrotron Based Research (1995 - Present)
  • W-184 Work Group, Western Soil Chemistry (1995 - Present)

Professional Education


  • Ph.D., University of Delaware, Soil & Environmental Chemistry (1992)
  • M.S., University of California, Soil Chemistry (1990)
  • B.S., California Polytechnic State University, Soil Science (1988)

Current Research and Scholarly Interests


Research
I am interested in the chemical and biological processes that govern the fate and transport (and thus cycling) of contaminants (such as arsenic) and nutrients (such as phosphate) within soils, sediments, and surface waters. My research group examines the chemical environments that develop as a result of both biotic and abiotic processes, and we strive to account for the physical complexity, inclusive of solute transport, within natural settings. Our particular emphasis is on reactions that change the oxidation state (redox reactions) and associated speciation of contaminants and nutrients, or solids that control their partitioning, within soils and sediments.

Teaching
I teach a range of courses on soils and soil processes that encompass their rates of development, unique features for plant growth, ability to filter contaminants, management for sustained agricultural productivity, and their sensitivity to human disturbance. I am also a co-instructor for a course on field research in Earth Systems.

Professional Activities
Faculty Director for Environmental Measurements Facility (2006-present); Terman Fellow, Stanford University (1999-2002); Stanford University Fellow (2004-06); National Research Council Committee for Defining Contaminant Bioavailability in Soils and Sediments (2000-02); Advisory Council and Faculty Representative for Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory (2007-present); Chemical Geology Editor for the special issue "Controls on Arsenic Transport in Near-Surface Aquatic Systems" (2006); NAS panel for Frontiers in Soil Science Research (2005); Panel organizer for DOE Environmental Remediation Science Program's "Influence of Coupled Biological, Chemical, and Physical Processes on Contaminant Fate and Transport" (2006)

2014-15 Courses


Journal Articles


  • Release of arsenic to deep groundwater in the Mekong Delta, Vietnam, linked to pumping-induced land subsidence PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA Erban, L. E., Gorelick, S. M., Zebker, H. A., Fendorf, S. 2013; 110 (34): 13751-13756

    Abstract

    Deep aquifers in South and Southeast Asia are increasingly exploited as presumed sources of pathogen- and arsenic-free water, although little is known of the processes that may compromise their long-term viability. We analyze a large area (>1,000 km(2)) of the Mekong Delta, Vietnam, in which arsenic is found pervasively in deep, Pliocene-Miocene-age aquifers, where nearly 900 wells at depths of 200-500 m are contaminated. There, intensive groundwater extraction is causing land subsidence of up to 3 cm/y as measured using satellite-based radar images from 2007 to 2010 and consistent with transient 3D aquifer simulations showing similar subsidence rates and total subsidence of up to 27 cm since 1988. We propose a previously unrecognized mechanism in which deep groundwater extraction is causing interbedded clays to compact and expel water containing dissolved arsenic or arsenic-mobilizing solutes (e.g., dissolved organic carbon and competing ions) to deep aquifers over decades. The implication for the broader Mekong Delta region, and potentially others like it across Asia, is that deep, untreated groundwater will not necessarily remain a safe source of drinking water.

    View details for DOI 10.1073/pnas.1300503110

    View details for Web of Science ID 000323271400029

  • Dependence of Arsenic Fate and Transport on Biogeochemical Heterogeneity Arising from the Physical Structure of Soils and Sediments JOURNAL OF ENVIRONMENTAL QUALITY Masue-Slowey, Y., Ying, S. C., Kocar, B. D., Pallud, C. E., Fendorf, S. 2013; 42 (4): 1119-1129
  • Morphological Adaptations for Digging and Climate-Impacted Soil Properties Define Pocket Gopher (Thomomys spp.) Distributions PLOS ONE Marcy, A. E., Fendorf, S., Patton, J. L., Hadly, E. A. 2013; 8 (5)

    Abstract

    Species ranges are mediated by physiology, environmental factors, and competition with other organisms. The allopatric distribution of five species of northern Californian pocket gophers (Thomomys spp.) is hypothesized to result from competitive exclusion. The five species in this environmentally heterogeneous region separate into two subgenera, Thomomys or Megascapheus, which have divergent digging styles. While all pocket gophers dig with their claws, the tooth-digging adaptations of subgenus Megascapheus allow access to harder soils and climate-protected depths. In a Northern Californian locality, replacement of subgenus Thomomys with subgenus Megascapheus occurred gradually during the Pleistocene-Holocene transition. Concurrent climate change over this transition suggests that environmental factors - in addition to soil - define pocket gopher distributional limits. Here we show 1) that all pocket gophers occupy the subset of less energetically costly soils and 2) that subgenera sort by percent soil clay, bulk density, and shrink-swell capacity (a mineralogical attribute). While clay and bulk density (without major perturbations) stay constant over decades to millennia, low precipitation and high temperatures can cause shrink-swell clays to crack and harden within days. The strong yet underappreciated interaction between soil and moisture on the distribution of vertebrates is rarely considered when projecting species responses to climatic change. Furthermore, increased precipitation alters the weathering processes that create shrink-swell minerals. Two projected outcomes of ongoing climate change-higher temperatures and precipitation-will dramatically impact hardness of soil with shrink-swell minerals. Current climate models do not include factors controlling soil hardness, despite its impact on all organisms that depend on a stable soil structure.

    View details for DOI 10.1371/journal.pone.0064935

    View details for Web of Science ID 000319385300008

    View details for PubMedID 23717675

  • Distributed microbially- and chemically-mediated redox processes controlling arsenic dynamics within Mn-/Fe-oxide constructed aggregates GEOCHIMICA ET COSMOCHIMICA ACTA Ying, S. C., Masue-Slowey, Y., Kocar, B. D., Griffis, S. D., Webb, S., Marcus, M. A., Francis, C. A., Fendorf, S. 2013; 104: 29-41
  • Silicate Mineral Impacts on the Uptake and Storage of Arsenic and Plant Nutrients in Rice (Oryza sativa L.) ENVIRONMENTAL SCIENCE & TECHNOLOGY Seyfferth, A. L., Fendorf, S. 2012; 46 (24): 13176-13183

    Abstract

    Arsenic-contaminated rice grain may threaten human health globally. Since H?AsO?? is the predominant As species found in paddy pore-waters, and H?SiO?? and H?AsO?? share an uptake pathway, silica amendments have been proposed to decrease As uptake and consequent As concentrations in grains. Here, we evaluated the impact of two silicate mineral additions differing in solubility (+Si(L), diatomaceous earth, 0.29 mM Si; +Si(H), Si-gel, 1.1 mM Si) to soils differing in mineralogy on arsenic concentration in rice. The +Si(L) addition either did not change or decreased As concentration in pore-water but did not change or increased grain-As levels relative to the (+As--Si) control. The +Si(H) addition increased As in pore-water, but it significantly decreased grain-As relative to the (+As--Si) control. Only the +Si(H) addition resulted in significant increases in straw- and husk-Si. Total grain- and straw-As was negatively correlated with pore-water Si, and the relationship differed between two soils exhibiting different mineralogy. These differing results are a consequence of competition between H?SiO?? and H?AsO?? for adsorption sites on soil solids and subsequent plant-uptake, and illustrate the importance of Si mineralogy on arsenic uptake.

    View details for DOI 10.1021/es3025337

    View details for Web of Science ID 000312432200020

    View details for PubMedID 23153302

  • Oxidation and competitive retention of arsenic between iron- and manganese oxides GEOCHIMICA ET COSMOCHIMICA ACTA Ying, S. C., Kocar, B. D., Fendorf, S. 2012; 96: 294-303
  • Intra-particle migration of mercury in granular polysulfide-rubber-coated activated carbon (PSR-AC) CHEMOSPHERE Kim, E., Masue-Slowey, Y., Fendorf, S., Luthy, R. G. 2012; 86 (6): 648-654

    Abstract

    The depth profile of mercuric ion after the reaction with polysulfide-rubber-coated activated carbon (PSR-AC) was investigated using micro-X-ray fluorescence (?-XRF) imaging techniques and mathematical modeling. The ?-XRF results revealed that mercury was concentrated at 0-100 ?m from the exterior of the particle after 3 months of treatment with PSR-AC in 10 ppm HgCl(2) aqueous solution. The ?-X-ray absorption near edge spectroscopic (?-XANES) analyses indicated HgS as a major mercury species, and suggested that the intra-particle mercury transport involved a chemical reaction with PSR polymer. An intra-particle mass transfer model was developed based on either a Langmuir sorption isotherm with liquid phase diffusion (Langmuir model) or a kinetic sorption with surface diffusion (kinetic sorption model). The Langmuir model predicted the general trend of mercury diffusion, although at a slower rate than observed from the ?-XRF map. A kinetic sorption model suggested faster mercury transport, which overestimated the movement of mercuric ions through an exchange reaction between the fast and slow reaction sites. Both ?-XRF and mathematical modeling results suggest mercury removal occurs not only at the outer surface of the PSR-AC particle but also at some interior regions due to a large PSR surface area within an AC particle.

    View details for DOI 10.1016/j.chemosphere.2011.11.012

    View details for Web of Science ID 000301096200014

    View details for PubMedID 22133913

  • Native and Non-Native Community Assembly through Edaphic Manipulation: Implications for Habitat Creation and Restoration RESTORATION ECOLOGY Bonebrake, T. C., Navratil, R. T., Boggs, C. L., Fendorf, S., Field, C. B., Ehrlichl, P. R. 2011; 19 (6): 709-716
  • Defining the distribution of arsenic species and plant nutrients in rice (Oryza sativa L.) from the root to the grain GEOCHIMICA ET COSMOCHIMICA ACTA Seyfferth, A. L., Webb, S. M., Andrews, J. C., Fendorf, S. 2011; 75 (21): 6655-6671
  • Geochemical Processes Governing the Fate and Transport of Chromium(III) and Chromium(VI) in Soils VADOSE ZONE JOURNAL Jardine, P. M., Mehlhorn, T. L., Bailey, W. B., Brooks, S. C., Fendorf, S., Gentry, R. W., Phelps, T. J., Saiers, J. E. 2011; 10 (3): 1058-1070
  • Competitive Microbially and Mn Oxide Mediated Redox Processes Controlling Arsenic Speciation and Partitioning ENVIRONMENTAL SCIENCE & TECHNOLOGY Ying, S. C., Kocar, B. D., Griffis, S. D., Fendorf, S. 2011; 45 (13): 5572-5579

    Abstract

    The speciation and partitioning of arsenic (As) in surface and subsurface environments are controlled, in part, by redox processes. Within soils and sediments, redox gradients resulting from mass transfer limitations lead to competitive reduction-oxidation reactions that drive the fate of As. Accordingly, the objective of this study was to determine the fate and redox cycling of As at the interface of birnessite (a strong oxidant in soil with a nominal formula of MnO(x), where x ? 2) and dissimilatory As(V)-reducing bacteria (strong reductant). Here, we investigate As reduction-oxidation dynamics in a diffusively controlled system using a Donnan reactor where birnessite and Shewanella sp. ANA-3 are isolated by a semipermeable membrane through which As migrates. Arsenic(III) injected into the reaction cell containing birnessite is rapidly oxidized to As(V). Arsenic(V) diffusing into the Shewanella chamber is then reduced to As(III), which subsequently diffuses back to the birnessite chamber, undergoing oxidation, and establishing a continuous cycling of As. However, we observe a rapid decline in the rate of As(III) oxidation owing to passivation of the birnessite surface. Modeling and experimental results show that high [Mn(II)] combined with increasing [CO(3)(2-)] from microbial respiration leads to the precipitation of rhodochrosite, which eventually passivates the Mn oxide surface, inhibiting further As(III) oxidation. Our results show that despite the initial capacity of birnessite to rapidly oxidize As(III), the synergistic effect of intense As(V) reduction by microorganisms and the buildup of reactive metabolites capable of passivating reactive mineral surfaces-here, birnessite-will produce (bio)geochemical conditions outside of those based on thermodynamic predictions.

    View details for DOI 10.1021/es200351m

    View details for Web of Science ID 000292075100019

    View details for PubMedID 21648436

  • Reduction of Uranium(VI) by Soluble Iron(II) Conforms with Thermodynamic Predictions ENVIRONMENTAL SCIENCE & TECHNOLOGY Du, X., Boonchayaanant, B., Wu, W., Fendorf, S., Bargar, J., Criddle, C. S. 2011; 45 (11): 4718-4725

    Abstract

    Soluble Fe(II) can reduce soluble U(VI) at rapid rates and in accordance with thermodynamic predictions. This was established by initially creating acidic aqueous solutions in which the sole oxidants were soluble U(VI) species and the sole reductants were soluble Fe(II) species. The pH of the solution was then increased by stepwise addition of OH(-), thereby increasing the potential for electron transfer from Fe(II) to U(VI). For each new pH value resulting from addition of base, values of ?G for the Fe(II)-mediated reduction of U(VI) were calculated using the computed distribution of U and Fe species and possible half reaction combinations. For initial conditions of pH 2.4 and a molar ratio of Fe(II) to U(VI) of 5:1 (1 mM Fe(II) and 0.2 mM U(VI)), ?G for U(VI) reduction was greater than zero, and U(VI) reduction was not observed. When sufficient OH(-) was added to exceed the computed equilibrium pH of 5.4, ?G for U(VI) reduction was negative and soluble Fe(II) species reacted with U(VI) in a molar ratio of ?2:1. X-ray absorption near-edge structure (XANES) spectroscopy confirmed production of U(IV). A decrease in pH confirmed production of acidity as the reaction advanced. As solution pH decreased to the equilibrium value, the rate of reaction declined, stopping completely at the predicted equilibrium pH. Initiation of the reaction at a higher pH resulted in a higher final ratio of U(IV) to U(VI) at equilibrium.

    View details for DOI 10.1021/es2006012

    View details for Web of Science ID 000291128700011

    View details for PubMedID 21553877

  • Dehalogenation of Polybrominated Diphenyl Ethers and Polychlorinated Biphenyl by Bimetallic, Impregnated, and Nanoscale Zerovalent Iron ENVIRONMENTAL SCIENCE & TECHNOLOGY Zhuang, Y., Ahn, S., Seyfferth, A. L., Masue-Slowey, Y., Fendorf, S., Luthy, R. G. 2011; 45 (11): 4896-4903

    Abstract

    Nanoscale zerovalent iron particles (nZVI), bimetallic nanoparticles (nZVI/Pd), and nZVI/Pd impregnated activated carbon (nZVI/Pd-AC) composite particles were synthesized and investigated for their effectiveness to remove polybrominated diphenyl ethers (PBDEs) and/or polychlorinated biphenyls (PCBs). Palladization of nZVI promoted the dehalogenation kinetics for mono- to tri-BDEs and 2,3,4-trichlorobiphenyl (PCB 21). Compared to nZVI, the iron-normalized rate constants for nZVI/Pd were about 2-, 3-, and 4-orders of magnitude greater for tri-, di-, and mono-BDEs, respectively, with diphenyl ether as a main reaction product. The reaction kinetics and pathways suggest an H-atom transfer mechanism. The reaction pathways with nZVI/Pd favor preferential removal of para-halogens on PBDEs and PCBs. X-ray fluorescence mapping of nZVI/Pd-AC showed that Pd mainly deposits on the outer part of particles, while Fe was present throughout the activated carbon particles. While BDE 21 was sorbed onto activated carbon composites quickly, debromination was slower compared to reaction with freely dispersed nZVI/Pd. Our XPS and chemical data suggest about 7% of the total iron within the activated carbon was zerovalent, which shows the difficulty with in-situ synthesis of a significant fraction of zerovalent iron in the microporous material. Related factors that likely hinder the reaction with nZVI/Pd-AC are the heterogeneous distribution of nZVI and Pd on activated carbon and/or immobilization of hydrophobic organic contaminants at the adsorption sites thereby inhibiting contact with nZVI.

    View details for DOI 10.1021/es104312h

    View details for Web of Science ID 000291128700035

    View details for PubMedID 21557574

  • Alteration of ferrihydrite reductive dissolution and transformation by adsorbed As and structural Al: Implications for As retention GEOCHIMICA ET COSMOCHIMICA ACTA Masue-Slowey, Y., Loeppert, R. H., Fendorf, S. 2011; 75 (3): 870-886
  • Influence of Natural Organic Matter on As Transport and Retention ENVIRONMENTAL SCIENCE & TECHNOLOGY Sharma, P., Rolle, M., Kocar, B., Fendorf, S., Kappler, A. 2011; 45 (2): 546-553

    Abstract

    Natural organic matter (NOM) can affect the behavior of arsenic within surface and subsurface environments. We used batch and column experiments to determine the effect of peat humic acids (PHA), groundwater fulvic acids (GFA), and a soil organic matter (SOM) extract on As sorption/transport in ferrihydrite-coated sand columns. A reactive transport model was used to quantitatively interpret the transport of As in flow-through column (breakthrough) experiments. We found that As(III) breakthrough was faster than As(V) by up to 18% (with OM) and 14% (without OM). The most rapid breakthrough occurred in systems containing SOM and GFA. Dialysis and ultrafiltration of samples from breakthrough experiments showed that in OM-containing systems, As was transported mostly as free (noncomplexed) dissolved As but also as ternary As-Fe-OM colloids and dissolved complexes. In OM-free systems, As was transported in colloidal form or as a free ion. During desorption, more As(III) desorbed (23-37%) than As(V) (10-16%), and SOM resulted in the highest and OM-free systems the lowest amount of desorption. Overall, our experiments reveal that (i) NOM can enhance transport/mobilization of As, (ii) different fractions of NOM are capable of As mobilization, and (iii) freshly extracted SOM (from a forest soil) had greater impact on As transport than purified GFA/PHA.

    View details for DOI 10.1021/es1026008

    View details for Web of Science ID 000286090500034

    View details for PubMedID 21142173

  • Transport Implications Resulting from Internal Redistribution of Arsenic and Iron within Constructed Soil Aggregates ENVIRONMENTAL SCIENCE & TECHNOLOGY Masue-Slowey, Y., Kocar, B. D., Jofre, S. A., Mayer, K. U., Fendorf, S. 2011; 45 (2): 582-588

    Abstract

    Soils are an aggregate-based structured media that have a multitude of pore domains resulting in varying degrees of advective and diffusive solute and gas transport. Consequently, a spectrum of biogeochemical processes may function at the aggregate scale that collectively, and coupled with solute transport, determine element cycling in soils and sediments. To explore how the physical structure impacts biogeochemical processes influencing the fate and transport of As, we examined temporal changes in speciation and distribution of As and Fe within constructed aggregates through experimental measurement and reactive transport simulations. Spherical aggregates were made with As(V)-bearing ferrihydrite-coated sand inoculated with Shewanella sp. ANA-3; aerated solute flow around the aggregate was then induced. Despite the aerated aggregate exterior, where As(V) and ferrihydrite persist as the dominant species, anoxia develops within the aggregate interior. As a result, As and Fe redox gradients emerge, and the proportion of As(III) and magnetite increases toward the aggregate interior. Arsenic(III) and Fe(II) produced in the interior migrate toward the aggregated exterior and result in coaccumulation of As and Fe(III) proximal to preferential flow paths as a consequence of oxygenic precipitation. The oxidized rind of aggregates thus serves as a barrier to As release into advecting pore-water, but also leads to be a buildup of this hazardous element at preferential flow boundaries that could be released upon shifting geochemical conditions.

    View details for DOI 10.1021/es1027663

    View details for Web of Science ID 000286090500039

    View details for PubMedID 21158450

  • Short-term fates of high sulfur inputs in Northern California vineyard soils NUTRIENT CYCLING IN AGROECOSYSTEMS Hinckley, E. S., Fendorf, S., Matson, P. 2011; 89 (1): 135-142
  • Competitive Mn-oxide and microbially mediated redox process controlling arsenic speciation and partitioning Environmental Science & Technology Ying, S. C., Kocar, B. D., Griffis, S., Fendorf, S. 2011; 45: 5572-5577

    View details for DOI 10.1021/es200351m

  • Effect of Uranium(VI) Speciation on Simultaneous Microbial Reduction of Uranium(VI) and Iron(III) JOURNAL OF ENVIRONMENTAL QUALITY Stewart, B. D., Amos, R. T., Fendorf, S. 2011; 40 (1): 90-97

    Abstract

    Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates whether it will reside in the aqueous or solid phase and thus plays an integral role in the mobility of uranium within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO2(2+) and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO. However, various factors within soils and sediments, such as U(VI) speciation and the presence of competitive electron acceptors, may limit biological reduction of U(VI). Here we examine simultaneous dissimilatory reduction of Fe(III) and U(VI) in batch systems containing dissolved uranyl acetate and ferrihydrite-coated sand. Varying amounts of calcium were added to induce changes in aqueous U(VI) speciation. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% in absence of Ca or ferrihydrite, but only 24% (with ferrihydrite) and 14% (without ferrihydrite) were removed for systems with 0.8 mM Ca. Dissimilatory reduction of Fe(III) and U(VI) proceed through different enzyme pathways within one type of organism. We quantified the rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concecentration (0-0.8 mM). The mathematical construct, implemented with the reactive transport code MIN3P, reveals predominant factors controlling rates and extent of uranium reduction in complex geochemical systems.

    View details for DOI 10.2134/jeq2010.0304

    View details for Web of Science ID 000285715300011

    View details for PubMedID 21488497

  • Immobilization of Hg(II) in water with polysulfide-rubber (PSR) polymer-coated activated carbon WATER RESEARCH Kim, E., Seyfferth, A. L., Fendorf, S., Luthy, R. G. 2011; 45 (2): 453-460

    Abstract

    An effective mercury removal method using polymer-coated activated carbon was studied for possible use in water treatment. In order to increase the affinity of activated carbon for mercury, a sulfur-rich compound, polysulfide-rubber (PSR) polymer, was effectively coated onto the activated carbon. The polymer was synthesized by condensation polymerization between sodium tetrasulfide and 1,2-dichloroethane in water. PSR-mercury interactions and Hg-S bonding were elucidated from x-ray photoelectron spectroscopy, and Fourier transform infra-red spectroscopy analyses. The sulfur loading levels were controlled by the polymer dose during the coating process and the total surface area of the activated carbon was maintained for the sulfur loading less than 2 wt%. Sorption kinetic studies showed that PSR-coated activated carbon facilitates fast reaction by providing a greater reactive surface area than PSR alone. High sulfur loading on activated carbon enhanced mercury adsorption contributing to a three orders of magnitude reduction in mercury concentration. ?-X-ray absorption near edge spectroscopic analyses of the mercury bound to activated carbon and to PSR on activated carbon suggests the chemical bond with mercury on the surface is a combination of Hg-Cl and Hg-S interaction. The pH effect on mercury removal and adsorption isotherm results indicate competition between protons and mercury for binding to sulfur at low pH.

    View details for DOI 10.1016/j.watres.2010.08.045

    View details for Web of Science ID 000286790500005

    View details for PubMedID 20965542

  • Influence of Uranyl Speciation and Iron Oxides on Uranium Biogeochemical Redox Reactions GEOMICROBIOLOGY JOURNAL Stewart, B. D., Amos, R. T., Nico, P. S., Fendorf, S. 2011; 28 (5-6): 444-456
  • Arsenic Localization, Speciation, and Co-Occurrence with Iron on Rice (Oryza sativa L.) Roots Having Variable Fe Coatings ENVIRONMENTAL SCIENCE & TECHNOLOGY Seyfferth, A. L., Webb, S. M., Andrews, J. C., Fendorf, S. 2010; 44 (21): 8108-8113

    Abstract

    Arsenic contamination of rice is widespread, but the rhizosphere processes influencing arsenic attenuation remain unresolved. In particular, the formation of Fe plaque around rice roots is thought to be an important barrier to As uptake, but the relative importance of this mechanism is not well characterized. Here we elucidate the colocalization of As species and Fe on rice roots with variable Fe coatings; we used a combination of techniques--X-ray fluorescence imaging, ?XANES, transmission X-ray microscopy, and tomography--for this purpose. Two dominant As species were observed in fine roots-inorganic As(V) and As(III) -with minor amounts of dimethylarsinic acid (DMA) and arsenic trisglutathione (AsGlu(3)). Our investigation shows that variable Fe plaque formation affects As entry into rice roots. In roots with Fe plaque, As and Fe were strongly colocated around the root; however, maximal As and Fe were dissociated and did not encapsulate roots that had minimal Fe plaque. Moreover, As was not exclusively associated with Fe plaque in the rice root system; Fe plaque does not coat many of the young roots or the younger portion of mature roots. Young, fine roots, important for solute uptake, have little to no iron plaque. Thus, Fe plaque does not directly intercept (and hence restrict) As supply to and uptake by rice roots but rather serves as a bulk scavenger of As predominantly near the root base.

    View details for DOI 10.1021/es101139z

    View details for Web of Science ID 000283484000024

    View details for PubMedID 20936818

  • Spatial and Temporal Variations of Groundwater Arsenic in South and Southeast Asia SCIENCE Fendorf, S., Michael, H. A., van Geen, A. 2010; 328 (5982): 1123-1127

    Abstract

    Over the past few decades, groundwater wells installed in rural areas throughout the major river basins draining the Himalayas have become the main source of drinking water for tens of millions of people. Groundwater in this region is much less likely to contain microbial pathogens than surface water but often contains hazardous amounts of arsenic--a known carcinogen. Arsenic enters groundwater naturally from rocks and sediment by coupled biogeochemical and hydrologic processes, some of which are presently affected by human activity. Mitigation of the resulting health crisis in South and Southeast Asia requires an understanding of the transport of arsenic and key reactants such as organic carbon that could trigger release in zones with presently low groundwater arsenic levels.

    View details for DOI 10.1126/science.1172974

    View details for Web of Science ID 000278104700034

    View details for PubMedID 20508123

  • Aggregate-scale spatial heterogeneity in reductive transformation of ferrihydrite resulting from coupled biogeochemical and physical processes GEOCHIMICA ET COSMOCHIMICA ACTA Pallud, C., Masue-Slowey, Y., Fendorf, S. 2010; 74 (10): 2811-2825
  • Impact of Uranyl-Calcium-Carbonato Complexes on Uranium(VI) Adsorption to Synthetic and Natural Sediments ENVIRONMENTAL SCIENCE & TECHNOLOGY Stewart, B. D., Mayes, M. A., Fendorf, S. 2010; 44 (3): 928-934

    Abstract

    Adsorption on soil and sediment solids may decrease aqueous uranium concentrations and limit its propensity for migration in natural and contaminated settings. Uranium adsorption will be controlled in large part by its aqueous speciation, with a particular dependence on the presence of dissolved calcium and carbonate. Here we quantify the impact of uranyl speciation on adsorption to both goethite and sediments from the Hanford Clastic Dike and Oak Ridge Melton Branch Ridgetop formations. Hanford sediments were preconditioned with sodium acetate and acetic acid to remove carbonate grains, and Ca and carbonate were reintroduced at defined levels to provide a range of aqueous uranyl species. U(VI) adsorption is directly linked to UO(2)(2+) speciation, with the extent of retention decreasing with formation of ternary uranyl-calcium-carbonato species. Adsorption isotherms under the conditions studied are linear, and K(d) values decrease from 48 to 17 L kg(-1) for goethite, from 64 to 29 L kg (-1) for Hanford sediments, and from 95 to 51 L kg(-1) for Melton Branch sediments as the Ca concentration increases from 0 to 1 mM at pH 7. Our observations reveal that, in carbonate-bearing waters, neutral to slightly acidic pH values ( approximately 5) and limited dissolved calcium are optimal for uranium adsorption.

    View details for DOI 10.1021/es902194x

    View details for Web of Science ID 000273950100015

    View details for PubMedID 20058915

  • Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite GEOCHIMICA ET COSMOCHIMICA ACTA Kocar, B. D., Borch, T., Fendorf, S. 2010; 74 (3): 980-994
  • Kinetic and Mechanistic Constraints on the Oxidation of Biogenic Uraninite by Ferrihydrite ENVIRONMENTAL SCIENCE & TECHNOLOGY Ginder-Vogel, M., Stewart, B., Fendorf, S. 2010; 44 (1): 163-169

    Abstract

    The oxidation state of uranium plays a major role in determining uranium mobility in the environment. Under anaerobic conditions, common metal respiring bacteria enzymatically reduce soluble U(VI) to U(IV), resulting in the formation of sparingly soluble UO(2(bio)) (biogenic uraninite). The stability of biologically precipitated uraninite is critical for determining the long-term fate of uranium and is not well characterized within soils and sediments. Here, we demonstrate that biogenic uraninite oxidation by ferrihydrite, an environmentally ubiquitous, disordered Fe(III) (hydr)oxide, appears to proceed through a soluble U(IV) intermediate and results in the concomitant production of Fe(II) and dissolved U(VI). Uraninite oxidation rates are accelerated under conditions that increase its solubility and decrease uraninite surface passivation, which include high bicarbonate concentration and pH values deviating from neutrality. Thus, our results demonstrate that UO(2(bio)) oxidation by Fe(III) (hydr)oxides is controlled by the rate of uraninite dissolution and that this process may limit uranium(IV) sequestration in the presence of Fe(III) (hydr)oxides.

    View details for DOI 10.1021/es902452u

    View details for Web of Science ID 000273267000030

    View details for PubMedID 20039747

  • Arsenic in South Asia Groundwater Geography Compass Benner, S. G., Fendorf, S. 2010; 4: 1532-1552
  • Microbial and metal water quality in rain catchments compared with traditional drinking water sources in the East Sepik Province, Papua New Guinea JOURNAL OF WATER AND HEALTH Horak, H. M., Chynoweth, J. S., Myers, W. P., Davis, J., Fendorf, S., Boehm, A. B. 2010; 8 (1): 126-138

    Abstract

    In Papua New Guinea, a significant portion of morbidity and mortality is attributed to water-borne diseases. To reduce incidence of disease, communities and non-governmental organizations have installed rain catchments to provide drinking water of improved quality. However, little work has been done to determine whether these rain catchments provide drinking water of better quality than traditional drinking water sources, and if morbidity is decreased in villages with rain catchments. The specific aim of this study was to evaluate the quality of water produced by rain catchments in comparison with traditional drinking water sources in rural villages in the East Sepik Province. Fifty-four water sources in 22 villages were evaluated for enterococci and Escherichia coli densities as well as 14 health-relevant metals. In addition, we examined how the prevalence of diarrhoeal illness in villages relates to the type of primary drinking water source. The majority of tested metals were below World Health Organization safety limits. Catchment water sources had lower enterococci and E. coli than other water sources. Individuals in villages using Sepik River water as their primary water source had significantly higher incidence of diarrhoea than those primarily using other water sources (streams, dug wells and catchments).

    View details for Web of Science ID 000275310700014

    View details for PubMedID 20009255

  • Spatial Patterns and Modeling of Reductive Ferrihydrite Transformation Observed in Artificial Soil Aggregates ENVIRONMENTAL SCIENCE & TECHNOLOGY Pallud, C., Kausch, M., Fendorf, S., Meile, C. 2010; 44 (1): 74-79

    Abstract

    Within soils, biogeochemical processes controlling elemental cycling are heterogeneously distributed owing, in large part, to the physical complexity of the media. Here we quantify how diffusive mass-transfer limitation at the soil aggregate scale controls the biogeochemical processes governing ferrihydrite reductive dissolution and secondary iron mineral formation. Artificial cm-scale aggregates made of ferrihydrite-coated sand inoculated with iron-reducing bacteria were placed in flow-through reactors, mimicking macro- and microporous soil environments. A reactive transport model was developed to delineate diffusively and advectively controlled regions, identify reaction zones and estimate kinetic parameters. Simulated iron (Fe) breakthrough-curves show good agreement with experimental results for a wide-range of flow rates and input lactate concentrations, with only a limited amount (< or =12%) of Fe lost in the reactor outflow over a 31 day period. Model simulations show substantial intra-aggregate, mm-scale radial variations in the secondary iron phase distributions, reproducing the trends observed experimentally where only limited transformation of ferrihydrite was found near the aggregate surface, whereas extensive formation of goethite/lepidocrocite and minor amounts of magnetite and/or siderite were observed toward the aggregate center. Our study highlights the important control of variations in transport intensities on microbially induced iron transformation at the soil aggregate scale.

    View details for DOI 10.1021/es901736t

    View details for Web of Science ID 000273267000017

    View details for PubMedID 20039736

  • Aggregate-Scale Heterogeneity in Iron (Hydr)oxide Reductive Transformations VADOSE ZONE JOURNAL Tufano, K. J., Benner, S. G., Mayer, K. U., Marcus, M. A., Nico, P. S., Fendorf, S. 2009; 8 (4): 1004-1012
  • Incorporation of Oxidized Uranium into Fe (Hydr)oxides during Fe(II) Catalyzed Remineralization ENVIRONMENTAL SCIENCE & TECHNOLOGY Nico, P. S., Stewart, B. D., Fendorf, S. 2009; 43 (19): 7391-7396

    Abstract

    The form of solid phase U after Fe(II) induced anaerobic remineralization of ferrihydrite in the presence of aqueous and absorbed U(VI) was investigated under both abiotic batch and biotic flow conditions. Experiments were conducted with synthetic ground waters containing 0.168 mM U(VI), 3.8 mM carbonate, and 3.0 mM Ca2+. In spite of the high solubility of U(VI) under these conditions, appreciable removal of U(VI) from solution was observed in both the abiotic and biotic systems. The majority of the removed U was determined to be substituted as oxidized U (U(VI) or U(V)) into the octahedral position of the goethite and magnetite formed during ferrihydrite remineralization. It is estimated that between 3 and 6% of octahedral Fe(III) centers in the new Fe minerals were occupied by U. This site specific substitution is distinct from the nonspecific U coprecipitation processes in which uranyl compounds, e.g., uranyl hydroxide or carbonate, are entrapped within newly formed Fe oxides. The prevalence of site specific U incorporation under both abiotic and biotic conditions and the fact that the produced solids were shown to be resistant to both extraction (30 mM KHCO3) and oxidation (air for 5 days) suggest the potential importance of sequestration in Fe oxides as a stable and immobile form of U in the environment.

    View details for DOI 10.1021/es900515q

    View details for Web of Science ID 000270136500039

    View details for PubMedID 19848151

  • Stability of Uranium Incorporated into Fe (Hydr)oxides under Fluctuating Redox Conditions ENVIRONMENTAL SCIENCE & TECHNOLOGY Stewart, B. D., Nico, P. S., Fendorf, S. 2009; 43 (13): 4922-4927

    Abstract

    Reaction pathways resulting in uranium-bearing solids that are stable (i.e., having limited solubility) under aerobic and anaerobic conditions will limit dissolved concentrations and migration of this toxin. Here, we examine the sorption mechanism and propensity for release of uranium reacted with Fe (hydr)oxides under cyclic oxidizing and reducing conditions. Upon reaction of ferrihydrite with Fe(II) under conditions where aqueous Ca-UO2-CO3 species predominate (3 mM Ca and 3.8 mM total CO3), dissolved uranium concentrations decrease from 0.16 mM to below detection limit (BDL) after 5-15 d, depending on the Fe(II) concentration. In systems undergoing 3 successive redox cycles (14 d of reduction, followed by 5 d of oxidation) and a pulsed decrease to 0.15 mM total CO3, dissolved uranium concentrations varied depending on the Fe(II) concentration during the initial and subsequent reduction phases. U concentrations resulting during the oxic "rebound" varied inversely with the Fe(II) concentration during the reduction cycle. Uranium removed from solution remains in the oxidized form and is found adsorbed onto and incorporated into the structure of newly formed goethite and magnetite. Our results reveal that the fate of uranium is dependent on anaerobic/ aerobic conditions, aqueous uranium speciation, and the fate of iron.

    View details for DOI 10.1021/es803317w

    View details for Web of Science ID 000267435500048

    View details for PubMedID 19673286

  • Thermodynamic Constraints on Reductive Reactions Influencing the Biogeochemistry of Arsenic in Soils and Sediments ENVIRONMENTAL SCIENCE & TECHNOLOGY Kocar, B. D., Fendorf, S. 2009; 43 (13): 4871-4877

    Abstract

    Arsenic is a widespread environmental toxin having devastating impacts on human health. A transition to anaerobic conditions is a key driver for promoting As desorption through either the reduction of As(V) or the reductive dissolution of Fe(III) (hydr)oxides. However, a disparity in the reported release sequence for As and Fe to the aqueous solution hinders our ability to determine the controlling factors liberating As to the aqueous environment. Accordingly, we performed a thermodynamic analysis of Fe, using a range of Fe-(hydr)oxides, and As reduction coupled with hydrogen, acetate, and lactate oxidation for a range of relevant field conditions. The favorability of sulfate reduction is also evaluated. Our results illustrate that As reduction is favorable over a wide-range of field conditions, and Fe reduction is differentially favorable depending on the buildup of metabolites (mainly Fe2+) and the Fe (hydr)oxide being reduced; reduction of As(V) is thermodynamically favorable under most environmental conditions and almost always more favorable than goethite and hematite reduction. Sulfate reduction is favorable over a range of conditions, and may occur concomitantly with Fe reduction depending on the Fe (hydr)oxides present. Thus, on a thermodynamic basis, the general sequence of microbial reduction should be As(V) followed by Fe(III) or sulfate.

    View details for DOI 10.1021/es8035384

    View details for Web of Science ID 000267435500040

    View details for PubMedID 19673278

  • Time-lapse geophysical imaging of soil moisture dynamics in tropical deltaic soils: An aid to interpreting hydrological and geochemical processes WATER RESOURCES RESEARCH Robinson, D. A., Lebron, I., Kocar, B., Phan, K., Sampson, M., Crook, N., Fendorf, S. 2009; 45
  • BIOGEOCHEMICAL PROCESSES CONTROLLING THE FATE AND TRANSPORT OF ARSENIC: IMPLICATIONS FOR SOUTH AND SOUTHEAST ASIAm ADVANCES IN AGRONOMY, VOLUME 104 Fendorf, S., Kocar, B. D. 2009; 104: 137-164
  • Incorporation of uranium(VI) into Fe(hydr)oxides during Fe(II) catalyzed remineralization Environmental Science & Technology Nico, P. S., Stewart, B. D., Fendorf, S.. 2009; 43: 7391-7396
  • Spatial patterns of iron transformations within artificial soil aggregates: Experimental and modeling analysis of diffusion limited iron cycling Environmental Science & Technology Pallud, C., Kausch, M., Fendorf, S., Meile, C. 2009; 43: 74-79
  • Reductive Processes Controlling Arsenic Retention: Revealing the Relative Importance of Iron and Arsenic Reduction ENVIRONMENTAL SCIENCE & TECHNOLOGY Tufano, K. J., Reyes, C., Saltikov, C. W., Fendorf, S. 2008; 42 (22): 8283-8289

    Abstract

    The fate and transport of arsenic is regulated, in part, by its strong affinity for iron (hydr)oxides. A transition from aerobic to anaerobic conditions resulting in concomitant reduction of both As(V) and iron (hydr)oxides can thus have a pronounced influence on As partitioning. However, it is presently unclear whether As desorption under anaerobic conditions results predominantly from a transformation from As(V) to As(III) or from mineralogical changes as a consequence of iron and manganese reduction. Here, we examine desorption of both As(III) and As(V) from ferrihydrite-, goethite-, and hematite-coated sand under hydrodynamic conditions. Furthermore, to resolve the relative role of Fe(III) and/or As(V) reduction in regulating dissolved As concentrations, we also examined As desorption from ferrihydrite- and goethite-coated sands presorbed with As(V) using wild type or mutants of Shewanella sp. ANA-3, capable of Fe(III)- and/or As(V)-reduction. We reveal substantial differences in As(III) and As(V) desorption from ferrihydrite, goethite, and hematite. Despite being adsorbed to a greater extent than As(V), As(III) is desorbed more rapidly and extensively from all oxides, suggesting weaker binding of As(III) than As(V). When As(V) and Fe(III) reduction are decoupled, As(V) reduction appears to be the dominant process controlling As release. Our results also suggest the importance of appreciating physical properties of specific Fe (hydr)oxides when predicting the potential for As desorption.

    View details for DOI 10.1021/es801059s

    View details for Web of Science ID 000260921400020

    View details for PubMedID 19068807

  • Groundwater flow in an arsenic-contaminated aquifer, Mekong Delta, Cambodia APPLIED GEOCHEMISTRY Benner, S. G., Polizzotto, M. L., Kocar, B. D., Ganguly, S., Phan, K., Ouch, K., Sampson, M., Fendorf, S. 2008; 23 (11): 3072-3087
  • Integrated biogeochemical and hydrologic processes driving arsenic release from shallow sediments to groundwaters of the Mekong delta APPLIED GEOCHEMISTRY Kocar, B. D., Polizzotto, M. L., Benner, S. G., Ying, S. C., Ung, M., Ouch, K., Samreth, S., Suy, B., Phan, K., Sampson, M., Fendorf, S. 2008; 23 (11): 3059-3071
  • Depositional influences on porewater arsenic in sediments of a mining-contaminated freshwater lake ENVIRONMENTAL SCIENCE & TECHNOLOGY Toevs, G., Morra, M. J., Winowiecki, L., Strawn, D., Polizzotto, M. L., Fendorf, S. 2008; 42 (18): 6823-6829

    Abstract

    Arsenic-containing minerals mobilized during mining activities and deposited to Lake Coeur d'Alene (CDA), Idaho sediments represent a potential source of soluble As to the overlying water. Our objective was to delineate the processes controlling porewater As concentrations within Lake CDA sediments. Sediment and porewater As concentrations were determined, and solid-phase As associations were probed using X-ray absorption near-edge structure (XANES) spectroscopy. Although maximum As in the sediment porewaters varied from 8.4 to 16.2 microM, As sorption on iron oxyhydroxides at the oxic sediment-water interface prevented flux to overlying water. Floods deposit sediment containing variable amounts of arsenopyrite (FeAsS), with majorfloods depositing large amounts of sediment that bury and preserve reduced minerals. Periods of lower deposition increase sediment residence times in the oxic zone, promoting oxidation of reduced minerals, SO4(2-) efflux, and formation of oxide precipitates. Depositional events bury oxides containing sorbed As, transitioning them into anoxic environments where they undergo dissolution, releasing As to the porewater. High Fe:S ratios limit the formation of arsenic sulfides in the anoxic zone. As a result of As sequestration at the sediment-water interface and its release upon burial, decreased concentrations of porewater As will not occur unless As-bearing erosional inputs are eliminated.

    View details for DOI 10.1021/es800937t

    View details for Web of Science ID 000259139400012

    View details for PubMedID 18853795

  • Near-surface wetland sediments as a source of arsenic release to ground water in Asia NATURE Polizzotto, M. L., Kocar, B. D., Benner, S. G., Sampson, M., Fendorf, S. 2008; 454 (7203): 505-U5

    Abstract

    Tens of millions of people in south and southeast Asia routinely consume ground water that has unsafe arsenic levels. Arsenic is naturally derived from eroded Himalayan sediments, and is believed to enter solution following reductive release from solid phases under anaerobic conditions. However, the processes governing aqueous concentrations and locations of arsenic release to pore water remain unresolved, limiting our ability to predict arsenic concentrations spatially (between wells) and temporally (future concentrations) and to assess the impact of human activities on the arsenic problem. This uncertainty is partly attributed to a poor understanding of groundwater flow paths altered by extensive irrigation pumping in the Ganges-Brahmaputra delta, where most research has focused. Here, using hydrologic and (bio)geochemical measurements, we show that on the minimally disturbed Mekong delta of Cambodia, arsenic is released from near-surface, river-derived sediments and transported, on a centennial timescale, through the underlying aquifer back to the river. Owing to similarities in geologic deposition, aquifer source rock and regional hydrologic gradients, our results represent a model for understanding pre-disturbance conditions for other major deltas in Asia. Furthermore, the observation of strong hydrologic influence on arsenic behaviour indicates that release and transport of arsenic are sensitive to continuing and impending anthropogenic disturbances. In particular, groundwater pumping for irrigation, changes in agricultural practices, sediment excavation, levee construction and upstream dam installations will alter the hydraulic regime and/or arsenic source material and, by extension, influence groundwater arsenic concentrations and the future of this health problem.

    View details for DOI 10.1038/nature07093

    View details for Web of Science ID 000257860300048

    View details for PubMedID 18650922

  • Confounding impacts of iron reduction on arsenic retention ENVIRONMENTAL SCIENCE & TECHNOLOGY Tufano, K. J., Fendorf, S. 2008; 42 (13): 4777-4783

    Abstract

    A transition from oxidizing to reducing conditions has long been implicated to increase aqueous As concentrations, for which reductive dissolution of iron (hydr)oxides is commonly implicated as the primary culprit. Confounding our understanding of processes controlling As retention, however, is that reductive transformation of ferrihydrite has recently been shown to promote As retention rather than release. To resolve the role iron phases have in regulating arsenic concentrations, here we examine As desorption from ferrihydrite-coated sands presorbed with As(III); experiments were performed at circumneutral pH under Fe-reducing conditions with the dissimilatory iron reducing bacterium Shewanella putrefaciens strain CN-32 over extended time periods. We reveal that with the initial phase of iron reduction, ferrihydrite undergoes transformation to secondary phases and increases As(III) retention (relative to abiotic controls). However, with increased reaction time, cessation of the phase transitions and ensuing reductive dissolution result in prolonged release of As(III) to the aqueous phase. Our results suggest that As(III) retention during iron reduction is temporally dependent on secondary precipitation of iron phases; during transformation to secondary phases, particularly magnetite, As(III) retention is enhanced even relative to oxidized systems. However, conditions that retard secondary transformation (more stable iron oxides or limited iron reducing bacterial activity), or prolonged anaerobiosis, will lead to both the dissolution of ferric (hydr)oxides and release of As(III) to the aqueous phase.

    View details for DOI 10.1021/es702625e

    View details for Web of Science ID 000257220600031

    View details for PubMedID 18678005

  • Changes in bacterial and archaeal community structure and functional diversity along a geochemically variable soil profile APPLIED AND ENVIRONMENTAL MICROBIOLOGY Hansel, C. M., Fendorf, S., Jardine, P. M., Francis, C. A. 2008; 74 (5): 1620-1633

    Abstract

    Spatial heterogeneity in physical, chemical, and biological properties of soils allows for the proliferation of diverse microbial communities. Factors influencing the structuring of microbial communities, including availability of nutrients and water, pH, and soil texture, can vary considerably with soil depth and within soil aggregates. Here we investigated changes in the microbial and functional communities within soil aggregates obtained along a soil profile spanning the surface, vadose zone, and saturated soil environments. The composition and diversity of microbial communities and specific functional groups involved in key pathways in the geochemical cycling of nitrogen, Fe, and sulfur were characterized using a coupled approach involving cultivation-independent analysis of both 16S rRNA (bacterial and archaeal) and functional genes (amoA and dsrAB) as well as cultivation-based analysis of Fe(III)-reducing organisms. Here we found that the microbial communities and putative ammonia-oxidizing and Fe(III)-reducing communities varied greatly along the soil profile, likely reflecting differences in carbon availability, water content, and pH. In particular, the Crenarchaeota 16S rRNA sequences are largely unique to each horizon, sharing a distribution and diversity similar to those of the putative (amoA-based) ammonia-oxidizing archaeal community. Anaerobic microenvironments within soil aggregates also appear to allow for both anaerobic- and aerobic-based metabolisms, further highlighting the complexity and spatial heterogeneity impacting microbial community structure and metabolic potential within soils.

    View details for DOI 10.1128/AEM.01787-07

    View details for Web of Science ID 000253792700037

    View details for PubMedID 18192411

  • Decreasing lead bioaccessibility in industrial and firing range soils with phosphate-based amendments Journal of Environmental Quality Mosely, R. A., Barnett, M. O., Stewart, M. A., Mehlhorn, T. L., Jardine, P. M., Ginder-Vogel, M., Fendorf, S. 2008; 37: 2116-2124
  • Speciation-dependent microbial reduction of uranium within iron-coated sands ENVIRONMENTAL SCIENCE & TECHNOLOGY Neiss, J., Stewart, B. D., Nico, P. S., Fendorf, S. 2007; 41 (21): 7343-7348

    Abstract

    Transport of uranium within surface and subsurface environments is predicated largely on its redox state. Uranyl reduction may transpire through either biotic (enzymatic) or abiotic pathways; in either case, reduction of U(VI) to U(IV) results in the formation of sparingly soluble UO2 precipitates. Biological reduction of U(VI), while demonstrated as prolific under both laboratory and field conditions, is influenced by competing electron acceptors (such as nitrate, manganese oxides, or iron oxides) and uranyl speciation. Formation of Ca-UO2-CO3 ternary complexes, often the predominate uranyl species in carbonate-bearing soils and sediments, decreases the rate of dissimilatory U(VI) reduction. The combined influence of uranyl speciation within a mineralogical matrix comparable to natural environments and under hydrodynamic conditions, however, remains unresolved. We therefore examined uranyl reduction by Shewanella putrefaciens within packed mineral columns of ferrihydrite-coated quartz sand under conditions conducive or nonconducive to Ca-UO2-CO3 species formation. The results are dramatic. In the absence of Ca, where uranyl carbonato complexes dominate, U(VI) reduction transpires and consumes all of the U(VI) within the influent solution (0.166 mM) over the first 2.5 cm of the flow field for the entirety of the 54 d experiment. Over 2 g of U is deposited during this reaction period, and despite ferrihydrite being a competitive electron acceptor, uranium reduction appears unabated for the duration of our experiments. By contrast, in columns with 4 mM Ca in the influent solution (0.166 mM uranyl), reduction (enzymatic or surface-bound Fe(III) mediated) appears absent and breakthrough occurs within 18 d (at a flow rate of 3 pore volumes per day). Uranyl speciation, and in particular the formation of ternary Ca-UO2-CO3 complexes, has a profound impact on U(VI) reduction and thus transport within anaerobic systems.

    View details for DOI 10.1021/es0706697

    View details for Web of Science ID 000250556100028

    View details for PubMedID 18044509

  • In situ bioreduction of uranium (VI) to submicromolar levels and reoxidation by dissolved oxygen ENVIRONMENTAL SCIENCE & TECHNOLOGY Wu, W., Carley, J., Luo, J., Ginder-Vogel, M. A., Cardenas, E., Leigh, M. B., Hwang, C., Kelly, S. D., Ruan, C., Wu, L., Van Nostrand, J., Gentry, T., Lowe, K., Mehlhorn, T., Carroll, S., Luo, W., Fields, M. W., Gu, B., Watson, D., Kemner, K. M., Marsh, T., Tiedje, J., Zhou, J., Fendorf, S., Kitanidis, P. K., Jardine, P. M., Criddle, C. S. 2007; 41 (16): 5716-5723

    Abstract

    Groundwater within Area 3 of the U.S. Department of Energy (DOE) Environmental Remediation Sciences Program (ERSP) Field Research Center at Oak Ridge, TN (ORFRC) contains up to 135 microM uranium as U(VI). Through a series of experiments at a pilot scale test facility, we explored the lower limits of groundwater U(VI) that can be achieved by in-situ biostimulation and the effects of dissolved oxygen on immobilized uranium. Weekly 2 day additions of ethanol over a 2-year period stimulated growth of denitrifying, Fe(III)-reducing, and sulfate-reducing bacteria, and immobilization of uranium as U(IV), with dissolved uranium concentrations decreasing to low levels. Following sulfite addition to remove dissolved oxygen, aqueous U(VI) concentrations fell below the U.S. Environmental Protection Agengy maximum contaminant limit (MCL) for drinking water (< 30/microg L(-1) or 0.126 microM). Under anaerobic conditions, these low concentrations were stable, even in the absence of added ethanol. However, when sulfite additions stopped, and dissolved oxygen (4.0-5.5 mg L(-1)) entered the injection well, spatially variable changes in aqueous U(VI) occurred over a 60 day period, with concentrations increasing rapidly from < 0.13 to 2.0 microM at a multilevel sampling (MLS) well located close to the injection well, but changing little at an MLS well located further away. Resumption of ethanol addition restored reduction of Fe(III), sulfate, and U(VI) within 36 h. After 2 years of ethanol addition, X-ray absorption near-edge structure spectroscopy (XANES) analyses indicated that U(IV) comprised 60-80% of the total uranium in sediment samples. Atthe completion of the project (day 1260), U concentrations in MLS wells were less than 0.1 microM. The microbial community at MLS wells with low U(VI) contained bacteria that are known to reduce uranium, including Desulfovibrio spp. and Geobacter spp., in both sediment and groundwater. The dominant Fe(III)-reducing species were Geothrix spp.

    View details for DOI 10.1021/es062657b

    View details for Web of Science ID 000248886000026

    View details for PubMedID 17874778

  • Genesis of hexavalent chromium from natural sources in soil and groundwater PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA Oze, C., Bird, D. K., Fendorf, S. 2007; 104 (16): 6544-6549

    Abstract

    Naturally occurring Cr(VI) has recently been reported in ground and surface waters. Rock strata rich in Cr(III)-bearing minerals, in particular chromite, are universally found in these areas that occur near convergent plate margins. Here we report experiments demonstrating accelerated dissolution of chromite and subsequent oxidation of Cr(III) to aqueous Cr(VI) in the presence of birnessite, a common manganese mineral, explaining the generation of Cr(VI) by a Cr(III)-bearing mineral considered geochemically inert. Our results demonstrate that Cr(III) within ultramafic- and serpentinite-derived soils/sediments can be oxidized and dissolved through natural processes, leading to hazardous levels of aqueous Cr(VI) in surface and groundwater.

    View details for DOI 10.1073/pnas.0701085104

    View details for Web of Science ID 000245869200012

    View details for PubMedID 17420454

  • Quantifying constraints imposed by calcium and iron on bacterial reduction of uranium(VI) JOURNAL OF ENVIRONMENTAL QUALITY Stewart, B. D., Neiss, J., Fendorf, S. 2007; 36 (2): 363-372

    Abstract

    Uranium is a redox active contaminant of concern to both human health and ecological preservation. In anaerobic soils and sediments, the more mobile, oxidized form of uranium (UO(2)(2+) and associated species) may be reduced by dissimilatory metal-reducing bacteria. Despite rapid reduction in controlled, experimental systems, various factors within soils or sediments may limit biological reduction of U(VI), inclusive of competing electron acceptors and alterations in uranyl speciation. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite, and hematite) varying in free energies of formation. Observed pseudo first-order rate coefficients for U(VI) reduction vary from 12 +/- 0.60 x 10(-3) h(-1) (0 mM Ca in the presence of goethite) to 2.0 +/- 0.10 x 10(-3) h(-1) (0.8 mM Ca in the presence of hematite). Nevertheless, dissolved Ca (at concentrations from 0.2 to 0.8 mM) decreases the extent of U(VI) reduction by approximately 25% after 528 h relative to rates without Ca present. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Ferrihydrite, in contrast, acts as a competitive electron acceptor and thus, like Ca, decreases uranium reduction. However, while ferrihydrite decreases U(VI) in solutions without Ca, with increasing Ca concentrations U(VI) reduction is enhanced in the presence of ferrihydrite (relative to its absence)-U(VI) reduction, in fact, becomes almost independent of Ca concentration. The quantitative framework described herein helps to predict the fate and transport of uranium within anaerobic environments.

    View details for DOI 10.2134/jeq2006.0058

    View details for Web of Science ID 000244979300003

    View details for PubMedID 17255623

  • Micro-scale heterogeneity in biogeochemical uranium cycling X-RAY ABSORPTION FINE STRUCTURE-XAFS13 Ginder-Vogel, M., Wu, W., Kelly, S., Criddle, C. S., Carley, J., Jardine, P., Kemner, K. A., Fendorf, S. 2007; 882: 190-192
  • Phosphate imposed limitations on biological reduction and alteration of ferrihydrite ENVIRONMENTAL SCIENCE & TECHNOLOGY Borch, T., Masue, Y., Kukkadapu, R. K., Fendorf, S. 2007; 41 (1): 166-172

    Abstract

    Biogeochemical transformation (inclusive of dissolution) of iron (hydr)oxides resulting from dissimilatory reduction has a pronounced impact on the fate and transport of nutrients and contaminants in subsurface environments. Despite the reactivity noted for pristine (unreacted) minerals, iron (hydr)oxides within native environments will likely have a different reactivity owing in part to changes in surface composition. Accordingly, here we explore the impact of surface modifications induced by phosphate adsorption on ferrihydrite reduction by Shewanella putrefaciens under static and advective flow conditions. Alterations in surface reactivity induced by phosphate changes the extent, decreasing Fe(Ill) reduction nearly linearly with increasing P surface coverage, and pathway of iron biomineralization. Magnetite is the most appreciable mineralization product while minor amounts of vivianite and green rust-like phases are formed in systems having high aqueous concentrations of phosphate, ferrous iron, and bicarbonate. Goethite and lepidocrocite, characteristic biomineralization products at low ferrous-iron concentrations, are inhibited in the presence of adsorbed phosphate. Thus, deviations in iron (hydr)oxide reactivity with changes in surface composition, such as those noted here for phosphate, need to be considered within natural environments.

    View details for DOI 10.1021/es060695p

    View details for Web of Science ID 000243124600030

    View details for PubMedID 17265943

  • Elucidating biogeochemical reduction of chromate via carbon amendments and soil sterilization GEOMICROBIOLOGY JOURNAL Bank, T. L., Vishnivetskaya, T. A., Jardine, P. M., Ginder-Vogel, M. A., Fendorf, S., Baldwin, M. E. 2007; 24 (2): 125-132
  • Reduction of Cr(VI) under acidic conditions by the facultative Fe(III)-reducing bacterium Acidiphilium cryptum ENVIRONMENTAL SCIENCE & TECHNOLOGY Cummings, D. E., Fendorf, S., Singh, N., Sani, R. K., Peyton, B. M., Magnuson, T. S. 2007; 41 (1): 146-152

    Abstract

    The potential for biological reduction of Cr(VI) under acidic conditions was evaluated with the acidophilic, facultatively metal-reducing bacterium Acidiphilium cryptum strain JF-5 to explore the role of acidophilic microorganisms in the Cr cycle in low-pH environments. An anaerobic suspension of washed A. cryptum cells rapidly reduced 50 microM Cr(VI) at pH 3.2; biological reduction was detected from pH 1.7-4.7. The reduction product, confirmed by XANES analysis, was entirely Cr(III) that was associated predominantly with the cell biomass (70-80%) with the residual residing in the aqueous phase. Reduction of Cr(VI) showed a pH optimum similar to that for growth and was inhibited by 5 mM HgCl2, suggesting that the reaction was enzyme-mediated. Introduction of O2 into the reaction medium slowed the reduction rate only slightly, whereas soluble Fe(III) (as ferric sulfate) increased the rate dramatically, presumably by the shuttling of electrons from bioreduced Fe(II) to Cr(VI) in a coupled biotic-abiotic cycle. Starved cells could not reduce Cr(VI) when provided as sole electron acceptor, indicating that Cr(VI) reduction is not an energy-conserving process in A. cryptum. We speculate, rather, that Cr(VI) reduction is used here as a detoxification mechanism.

    View details for DOI 10.1021/es061333k

    View details for Web of Science ID 000243124600027

    View details for PubMedID 17265940

  • Contrasting effects of dissimilatory iron(III) and arsenic(V) reduction on arsenic retention and transport ENVIRONMENTAL SCIENCE & TECHNOLOGY Kocar, B. D., Herbel, M. J., Tufano, K. J., Fendorf, S. 2006; 40 (21): 6715-6721

    Abstract

    Reduction of arsenate As(V) and As-bearing Fe (hydr)- oxides have been proposed as dominant pathways of As release within soils and aquifers. Here we examine As elution from columns loaded with ferrihydrite-coated sand presorbed with As(V) or As(III) at circumneutral pH upon Fe and/or As reduction; biotic stimulated reduction is then compared to abiotic elution. Columns were inoculated with Shewanella putrefaciens strain CN-32 or Sulfurospirillum barnesii strain SES-3, organisms capable of As (V) and Fe (III) reduction, or Bacillus benzoevorans strain HT-1, an organism capable of As(V) but not Fe(III) reduction. On the basis of equal surface coverages, As(III) elution from abiotic columns exceeded As(V) elution by a factor of 2; thus, As(III) is more readily released from ferrihydrite under the imposed reaction conditions. Biologically mediated Asreduction induced by B. benzoevorans enhances the release of total As relative to As (V) under abiotic conditions. However, under Fe reducing conditions invoked by either S. barnesii or S. putrefaciens, approximately three times more As (V or III) was retained within column solids relative to the abiotic experiments, despite appreciable decreases in surface area due to biotransformation of solid phases. Enhanced As sequestration upon ferrihydrite reduction is consistent with adsorption or incorporation of As into biotransformed solids. Our observations indicate that As retention and release from Fe (hydr)oxide(s) is controlled by complex pathways of Fe biotransformation and that reductive dissolution of As-bearing ferrihydrite can promote As sequestration rather than desorption under conditions examined here.

    View details for DOI 10.1021/es061540k

    View details for Web of Science ID 000241628800036

    View details for PubMedID 17144301

  • Heterogeneous response to biostimulation for U(VI) reduction in replicated sediment microcosms BIODEGRADATION Nyman, J. L., Marsh, T. L., Ginder-Vogel, M. A., Gentile, M., Fendorf, S., Criddle, C. 2006; 17 (4): 303-316

    Abstract

    A field-scale experiment to assess biostimulation of uranium reduction is underway at the Natural and Accelerated Bioremediation Research Field Research Center (FRC) in Oak Ridge, Tennessee. To simulate the field experiment, we established replicate batch microcosms containing well-mixed contaminated sediment from a well within the FRC treatment zone, and we added an inoculum from a pilot-scale fluidized bed reactor representing the inoculum in the field experiment. After reduction of nitrate, both sulfate and soluble U(VI) concentration decreased. X-ray absorption near edge structure (XANES) spectroscopy confirmed formation of U(IV) in sediment from biostimulated microcosms, but did not detect reduction of solid-phase Fe(III). Two to three fragments dominated terminal restriction fragment length polymorphism (T-RFLP) profiles of the 16S rDNA gene. Comparison to a clone library indicated these fragments represented denitrifying organisms related to Acidovorax, and Acidovorax isolates from the inoculum were subsequently shown to reduce U(VI). Investigation using the T-RFLP Analysis Program (TAP T-RFLP) and chemical analyses detected the presence and activity of fermenting and sulfate-reducing bacteria after 2 weeks. These organisms likely contributed to uranium reduction. In some microcosms, soluble U(VI) concentration leveled off or rebounded, indicating microbial and/or mineralogical heterogeneity among samples. Sulfate, acetate, and ethanol were depleted only in those microcosms exhibiting a rebound in soluble U(VI). This suggests that rates of U(VI) desorption can exceed rates of U(VI) reduction when sulfate-reducing bacteria become substrate-limited. These observations underscore the importance of effective chemical delivery and the role of serial and parallel processes in uranium reduction.

    View details for DOI 10.1007/s10532-005-9000-3

    View details for Web of Science ID 000238773600002

    View details for PubMedID 16491308

  • Pilot-scale in situ bioremedation of uranium in a highly contaminated aquifer. 2. Reduction of U(VI) and geochemical control of U(VI) bioavailability ENVIRONMENTAL SCIENCE & TECHNOLOGY Wu, W., Carley, J., Gentry, T., Ginder-Vogel, M. A., Fienen, M., Mehlhorn, T., Yan, H., Caroll, S., Pace, M. N., Nyman, J., Luo, J., Gentile, M. E., Fields, M. W., Hickey, R. F., Gu, B., Watson, D., Cirpka, O. A., Zhou, J., Fendorf, S., Kitanidis, P. K., Jardine, P. M., Criddle, C. S. 2006; 40 (12): 3986-3995

    Abstract

    In situ microbial reduction of soluble U(VI) to sparingly soluble U(IV) was evaluated at the site of the former S-3 Ponds in Area 3 of the U.S. Department of Energy Natural and Accelerated Bioremediation Research Field Research Center, Oak Ridge, TN. After establishing conditions favorable for bioremediation (Wu, et al. Environ. Sci. Technol. 2006, 40, 3988-3995), intermittent additions of ethanol were initiated within the conditioned inner loop of a nested well recirculation system. These additions initially stimulated denitrification of matrix-entrapped nitrate, but after 2 months, aqueous U levels fell from 5 to approximately 1 microM and sulfate reduction ensued. Continued additions sustained U(VI) reduction over 13 months. X-ray near-edge absorption spectroscopy (XANES) confirmed U(VI) reduction to U(IV) within the inner loop wells, with up to 51%, 35%, and 28% solid-phase U(IV) in sediment samples from the injection well, a monitoring well, and the extraction well, respectively. Microbial analyses confirmed the presence of denitrifying, sulfate-reducing, and iron-reducing bacteria in groundwater and sediments. System pH was generally maintained at less than 6.2 with low bicarbonate level (0.75-1.5 mM) and residual sulfate to suppress methanogenesis and minimize uranium mobilization. The bioavailability of sorbed U(VI) was manipulated by addition of low-level carbonate (< 5 mM) followed by ethanol (1-1.5 mM). Addition of low levels of carbonate increased the concentration of aqueous U, indicating an increased rate of U desorption due to formation of uranyl carbonate complexes. Upon ethanol addition, aqueous U(VI) levels fell, indicating that the rate of microbial reduction exceeded the rate of desorption. Sulfate levels simultaneously decreased, with a corresponding increase in sulfide. When ethanol addition ended but carbonate addition continued, soluble U levels increased, indicating faster desorption than reduction. When bicarbonate addition stopped, aqueous U levels decreased, indicating adsorption to sediments. Changes in the sequence of carbonate and ethanol addition confirmed that carbonate-controlled desorption increased bioavailability of U(VI) for reduction.

    View details for DOI 10.1021/es051960u

    View details for Web of Science ID 000238217200052

    View details for PubMedID 16830572

  • Thermodynamic constraints on the oxidation of biogenic UO2 by Fe(III) (hydr) oxides ENVIRONMENTAL SCIENCE & TECHNOLOGY Ginder-Vogel, M., Criddle, C. S., Fendorf, S. 2006; 40 (11): 3544-3550

    Abstract

    Uranium mobility in the environment is partially controlled by its oxidation state, where it exists as either U(VI) or U(IV). In aerobic environments, uranium is generally found in the hexavalent form, is quite soluble, and readily forms complexes with carbonate and calcium. Under anaerobic conditions, common metal respiring bacteria can reduce soluble U(VI) species to sparingly soluble UO2 (uraninite); stimulation of these bacteria, in fact, is being explored as an in situ uranium remediation technique. However, the stability of biologically precipitated uraninite within soils and sediments is not well characterized. Here we demonstrate that uraninite oxidation by Fe(III) (hydr)oxides is thermodynamically favorable under limited geochemical conditions. Our analysis reveals that goethite and hematite have a limited capacity to oxidize UO2(biogenic) while ferrihydrite can lead to UO2(biogenic) oxidation. The extent of UO2(biogenic) oxidation by ferrihydrite increases with increasing bicarbonate and calcium concentration, but decreases with elevated Fe(II)(aq) and U(VI)(aq) concentrations. Thus, our results demonstrate that the oxidation of UO2(biogenic) by Fe(III) (hydr)oxides may transpire under mildly reducing conditions when ferrihydrite is present.

    View details for DOI 10.1021/es052305p

    View details for Web of Science ID 000237921200023

    View details for PubMedID 16786692

  • Introduction: Controls on arsenic transport in near-surface aquatic systems CHEMICAL GEOLOGY Ford, R. G., Fendorf, S., Wilkin, R. T. 2006; 228 (1-3): 1-5
  • Metal(loid) diagenesis in mine-impacted sediments of Lake Coeur d'Alene, Idaho ENVIRONMENTAL SCIENCE & TECHNOLOGY Toevs, G. R., Morra, M. J., Polizzotto, M. L., Strawn, D. G., Bostick, B. C., Fendorf, S. 2006; 40 (8): 2537-2543

    Abstract

    Mining activity along the South Fork of the Coeur d' Alene River in northern Idaho has resulted in fluvial mine tailings enriched in Pb, As, Ag, Sb, Hg, Cd, and Zn deposited on the lakebed of Lake Coeur d'Alene, thus serving as a potential benthic source of inorganic contaminants. Our objective was to characterize the dominant solid phase materials and diagenetic processes controlling metal(loid) solubilities, and thus their potential release to the overlying water column. Aqueous and solid concentrations of metal(loid) contaminants were examined along with distinct species of Fe and S within sediments and interstitial water. A gradient from oxic conditions at the sediment-water interface to anoxic conditions below 15 cm exists at all sites, resulting in a dynamic redox environment that controls the partitioning of contaminants. Fluvial deposition from frequent seasonal flood events bury ferric oxides residing at the sediment-water interface leading to reductive dissolution as they transition to the anoxic zone, consequently releasing associated metal(loids) to the interstitial water. Insufficient sulfur limits the formation of sulfidic minerals, but high carbonate content of this mining region buffers pH and promotes formation of siderite. Diagenetic reactions create chemical gradients encouraging the diffusion of metal(loids) toward the sediment--water interface, thereby, increasing the potential for release into the overlying water.

    View details for DOI 10.1021/es051781c

    View details for Web of Science ID 000236992700012

    View details for PubMedID 16683589

  • Arsenic cycling within surface and subsurface environments: Impact of iron mineralogy and bioreduction processes Chemical Geology Herbel, M., Fendorf, S. 2006; 228: 16-32
  • Pilot-scale bioremediation of uranium in a highly contaminated aquifer II: Reduction of U(VI) and geochemical control of U(VI) bioavailability Environmental Science & Technology Wu, W., Carley, J., Gentry, T., Ginder-Vogel, M. A., Fienen, M., Mehlhorn, T., Yan, H., Carroll, S., Nyman, J., Luo, J., Gentile, M. E., Fields, M. W., Hickey, R. F., Watson, D., Cirpka, O. A., Fendorf, S., Zhou, J., Kitanidis, P., Jardine, P. M., Criddle, C. S. 2006; 40: 3986-3995
  • Processes conducive to the release and transport of arsenic into aquifers of Bangladesh PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA Polizzotto, M. L., Harvey, C. F., Sutton, S. R., Fendorf, S. 2005; 102 (52): 18819-18823

    Abstract

    Arsenic is a contaminant in the groundwater of Holocene aquifers in Bangladesh, where approximately 57 million people drink water with arsenic levels exceeding the limits set by the World Health Organization. Although arsenic is native to the sediments, the means by which it is released to groundwater remains unresolved. Contrary to the current paradigm, ferric (hydr)oxides appear to dominate the partitioning of arsenic in the near surface but have a limited impact at aquifer depths where wells extract groundwater with high arsenic concentrations. We present a sequence of evidence that, taken together, suggest that arsenic may be released in the near surface and then transported to depth. We establish that (i) the only portion of the sediment profile with conditions destabilizing to arsenic in our analysis is in the surface or near-surface environment; (ii) a consistent input of arsenic via sediment deposition exists; (iii) retardation of arsenic transport is limited in the aquifers; and (iv) groundwater recharge occurs at a rate sufficient to necessitate continued input of arsenic to maintain observed concentrations. Our analyses thus lead to the premise that arsenic is liberated in surface and near-surface sediments through cyclic redox conditions and is subsequently transported to well depth. Influx of sediment and redox cycling provide a long-term source of arsenic that when liberated in the near surface is only weakly partitioned onto sediments deeper in the profile and is transported through aquifers by groundwater recharge.

    View details for DOI 10.1073/pna5.0509539103

    View details for Web of Science ID 000234350000010

    View details for PubMedID 16357194

  • Chromate reduction and retention processes within arid subsurface environments ENVIRONMENTAL SCIENCE & TECHNOLOGY Ginder-Vogel, M., Borch, T., Mayes, M. A., Jardine, P. M., Fendorf, S. 2005; 39 (20): 7833-7839

    Abstract

    Chromate is a widespread contaminantthat has deleterious impacts on human health, the mobility and toxicity of which are diminished by reduction to Cr(III). While biological and chemical reduction reactions of Cr(VI) are well resolved, reduction within natural sediments, particularly of arid environments, remains poorly described. Here, we examine chromate reduction within arid sediments from the Hanford, WA site, where Fe(III) (hydr)oxide and carbonate coatings limit mineral reactivity. Chromium(VI) reduction by Hanford sediments is negligible unless pretreated with acid; acidic pretreatment of packed mineral beds having a Cr(VI) feed solution results in Cr(III) associating with the minerals antigorite and lizardite in addition to magnetite and Fe(II)-bearing clay minerals. Highly alkaline conditions (pH > 14), representative of conditions near high-level nuclearwaste tanks, result in Fe(II) dissolution and concurrent Cr(VI) reduction. Additionally, Cr(III) and Cr(VI) are found associated with portlandite, suggesting a secondary mechanism for chromium retention at high pH. Thus, mineral reactivity is limited within this arid environment and appreciable reduction of Cr(VI) is restricted to highly alkaline conditions resulting near leaking radioactive waste disposal tanks.

    View details for DOI 10.1021/es050535y

    View details for Web of Science ID 000232758400015

    View details for PubMedID 16295844

  • Adsorption, oxidation, and bioaccessibility of As(III) in soils ENVIRONMENTAL SCIENCE & TECHNOLOGY Yang, J. K., Barnett, M. O., Zhuang, J. L., Fendorf, S. E., Jardine, P. M. 2005; 39 (18): 7102-7110

    Abstract

    At As-contaminated sites, where the ingestion of soil by children is typically the critical human-health exposure pathway, information on the bioavailability of soil-bound As is often limited. The influence of various soil physical and chemical properties (iron and manganese oxides, pH, cation exchange capacity, total inorganic and organic carbon, and particle size) on As(III) adsorption, sequestration, bioaccessibility (as a surrogate for oral bioavailability), and oxidation was investigated in 36 well-characterized soils by use of a physiologically based extraction test (PBET). These results were compared to an earlier published study with As(V) on the same set of soils. The properties of the soils were able to explain >80% of the variability in the adsorption and sequestration (as measured by the reduction in bioaccessibility over time) of As(III) in these soils. The initial bioaccessibility of As(III) was significantly higher than the initial bioaccessibility of As(V) on the same set of soils. However, over a 6-month period of aerobic aging, a significant portion of the solid-phase As(III) on these soils was oxidized to As(V), decreasing its bioaccessibility markedly. A multivariable linear regression model previously developed to predict the steady-state bioaccessibility of As(V) in soils was able to predict the bioaccessibility in As(III)-spiked soils within a root-mean-square error (RMSE) of 16.8%. Generally, soils having a higher iron oxide content and lower soil pH exhibited lower bioaccessibility. This model was also able to predict the in vivo bioavailability of As in contaminated soils previously used in an independent juvenile swine dosing trial within an RMSE of 15.5%, providing a greatly improved yet conservative estimate of bioavailability relative to the typical default assumption of 100%. However, the model was not able to accurately predict the bioavailability of As in a different set of contaminated soils previously used in an independent Cebus monkey dosing trial, consistently overpredicting the bioavailability, resulting in an RMSE of 42.7%. This model can be used to provide an initial estimate of As bioavailability in soil to aid in screening sites and justifying expensive site-specific animal feeding studies. Further, as the model is based on major soil properties, the resulting estimates are valid as long as the major soil properties do not change, thus providing some confidence in the long-term applicability of the estimates.

    View details for DOI 10.1021/es0481474

    View details for Web of Science ID 000231941700030

    View details for PubMedID 16201635

  • Competing Fe(II)-induced mineralization pathways of ferrihydrite ENVIRONMENTAL SCIENCE & TECHNOLOGY Hansel, C. M., Benner, S. G., Fendorf, S. 2005; 39 (18): 7147-7153

    Abstract

    Owing to its high surface area and intrinsic reactivity, ferrihydrite serves as a dominant sink for numerous metals and nutrients in surface environments and is a potentially important terminal electron acceptor for microbial respiration. Introduction of Fe (II), by reductive dissolution of Fe(III) minerals, for example, converts ferrihydrite to Fe phases varying in their retention and reducing capacity. While Fe(II) concentration is the master variable dictating secondary mineralization pathways of ferrihydrite, here we reveal thatthe kinetics of conversion and ultimate mineral assemblage are a function of competing mineralization pathways influenced by pH and stabilizing ligands. Reaction of Fe(II) with ferrihydrite results in the precipitation of goethite, lepidocrocite, and magnetite. The three phases vary in their precipitation extent, rate, and residence time, all of which are primarily a function of Fe(II) concentration and ligand type (Cl, SO4, CO3). While lepidocrocite and goethite precipitate over a large Fe(II) concentration range, magnetite accumulation is only observed at surface loadings greater than 1.0 mmol Fe(II)/g ferrihydrite (in the absence of bicarbonate). Precipitation of magnetite induces the dissolution of lepidocrocite (presence of Cl) or goethite (presence of SO4), allowing for Fe(III)-dependent crystal growth. The rate of magnetite precipitation is a function of the relative proportions of goethite to lepidocrocite; the lower solubility of the former Fe (hydr)oxide slows magnetite precipitation. A one unit pH deviation from 7, however, either impedes (pH 6) or enhances (pH 8) magnetite precipitation. In the absence of magnetite nucleation, lepidocrocite and goethite continue to precipitate at the expense of ferrihydrite with near complete conversion within hours, the relative proportions of the two hydroxides dependent upon the ligand present. Goethite also continues to precipitate at the expense of lepidocrocite in the absence of chloride. In fact, the rate and extent of both goethite and magnetite precipitation are influenced by conditions conducive to the production and stability of lepidocrocite. Thus, predicting the secondary mineralization of ferrihydrite, a process having sweeping influences on contaminant/nutrient dynamics, will need to take into consideration kinetic restraints and transient precursor phases (e.g., lepidocrocite) that influence ensuing reaction pathways.

    View details for DOI 10.1021/es050666z

    View details for Web of Science ID 000231941700036

    View details for PubMedID 16201641

  • Effects of a diel oxygen cycle on nitrogen transformations and greenhouse gas emissions in a eutrophied subtropical stream AQUATIC SCIENCES Harrison, J. A., Matson, P. A., Fendorf, S. E. 2005; 67 (3): 308-315
  • Bioreduction of uranium in a contaminated soil column ENVIRONMENTAL SCIENCE & TECHNOLOGY Gu, B. H., Wu, W. M., Ginder-Vogel, M. A., Yan, H., Fields, M. W., Zhou, J., Fendorf, S., Criddle, C. S., Jardine, P. M. 2005; 39 (13): 4841-4847

    Abstract

    The bioreduction of soluble uranium [U(VI)] to sparingly soluble U(IV) species is an attractive remedial technology for contaminated soil and groundwater due to the potential for immobilizing uranium and impeding its migration in subsurface environments. This manuscript describes a column study designed to simulate a three-step strategy proposed for the remediation of a heavily contaminated site at the U.S. Department of Energy's NABIR Field Research Center in Oak Ridge, TN. The soil is contaminated with high concentrations of uranium, aluminum, and nitrate and has a low, highly buffered pH (approximately 3.5). Steps proposed for remediation are (i) flushing to remove nitrate and aluminum, (ii) neutralization to establish pH conditions favorable for biostimulation, and (iii) biostimulation for U(VI) reduction. We simulated this sequence using a packed soil column containing undisturbed aggregates of U(VI)-contaminated saprolite that was flushed with an acidified salt solution (pH 4.0), neutralized with bicarbonate (60 mM), and then biostimulated by adding ethanol. The column was operated anaerobically in a closed-loop recirculation setup. However, during the initial month of biostimulation, ethanol was not utilized, and U(VI) was not reduced. A bacterial culture enriched from the site groundwaterwas subsequently added, and the consumption of ethanol coupled with sulfate reduction immediately ensued. The aqueous concentration of U(VI) initially increased, evidently because of the biological production of carbonate, a ligand known to solubilize uranyl. After approximately 50 days, aqueous U(VI) concentrations rapidly decreased from approximately 17 to <1 mg/L. At the conclusion of the experiment,the presence of reduced solid phase U(IV) was confirmed using X-ray absorption near edge structure spectroscopy. The results indicate that bioreduction to immobilize uranium is potentially feasible at this site; however, the stability of the reduced U(IV) and its potential reoxidation will require further investigation, as do the effects of groundwater chemistry and competitive microbial processes, such as methanogenesis.

    View details for Web of Science ID 000230245500032

    View details for PubMedID 16053082

  • Ca-UO2-CO3 complexation - Implications for Bioremediation of U(VI) PHYSICA SCRIPTA Kelly, S. D., Kemner, K. M., Brooks, S. C., Fredrickson, J. K., Carroll, S. L., Kennedy, D. W., Zachara, J. M., Plymale, A. E., Fendorf, S. 2005; T115: 915-917
  • Transformation and transport of arsenic within ferric hydroxide coated sands upon dissimilatory reducing bacterial activity ADVANCES IN ARSENIC RESEARCH Herbel, M., Fendorf, S. 2005; 915: 77-90
  • Temporal changes in soil partitioning and bioaccessibility of arsenic, chromium, and lead JOURNAL OF ENVIRONMENTAL QUALITY Fendorf, S., La Force, M. J., Li, G. C. 2004; 33 (6): 2049-2055

    Abstract

    The hazard imposed by trace element contaminants within soils is dependent on their ability to migrate into water systems and their availability for biological uptake. The degree to which a contaminant may dissociate from soil solids and become available to a target organism (i.e., bioaccessibility) is therefore a determining risk factor. We used a physiologically based extraction test (PBET) to estimate the bioaccessible fraction of arsenic-, chromium-, and lead-amended soil. We investigated soils from the A and B horizons of the Melton Valley series, obtained from Oak Ridge National Laboratory site, to address temporal changes in bioaccessibility. Additionally, common extractions that seek to define reactive pools of metals were employed and their correlation to PBET levels evaluated. With the exception of Pb amended to the A horizon, all other treatments exhibited an exponential decrease in bioaccessibility with incubation time. The bioaccessible fraction was less than 0.2 mg kg(-1) within 30 d of incubation for As and Cr in the A horizon and for As and Pb within the B horizon; Cr in the B horizon declined to nearly 0.3 mg kg(-1) within 100 d of aging. The exchangeable fraction declined with incubation period and, with the exception of Pb, was highly correlated with the decline in bioaccessibility. Our results demonstrate limited bioaccessibility in all but one case and the need to address both short-term temporal changes and, most importantly, the soil physiochemical properties. They further reveal the importance of incubation time on the reactivity of such trace elements.

    View details for Web of Science ID 000225240900010

    View details for PubMedID 15537927

  • Chemical structure of arsenic and chromium in CCA-treated wood: Implications of environmental weathering ENVIRONMENTAL SCIENCE & TECHNOLOGY Nico, P. S., Fendorf, S. E., Lowney, Y. W., Holm, S. E., Ruby, M. V. 2004; 38 (19): 5253-5260

    Abstract

    Chromated copper arsenate (CCA) has been used to treat lumber for over 60 years to increase the expected lifetime of CCA-treated wood. Because of the toxicity of the arsenic and chromium used in CCA treatment, regulatory and public attention has become focused on the potential risks from this exposure source. In particular, exposure of children to arsenic from CCA-treated wood used in decks and play sets has received considerable attention. X-ray Absorption Spectroscopy (XAS) was used to evaluate the chemical structure of As and Cr in three samples of CCA-treated materials: newly treated wood, aged wood (5 years as decking), and dislodgeable residue from aged (1-4 years as decking) CCA-treated wood. The form of the Cr and As in CCA-treated material is the same in fresh and aged samples, and between treated wood and dislodged residue. In all cases, the dominant oxidation state of the two elements is As(V) and Cr(III), and the local chemical environment of the two elements is best represented as a Cr/As cluster consisting of a Cr dimer bridged by an As(V) oxyanion. Long-term stability of the As/Cr cluster is suggested by its persistence from the new wood through the aged wood and the dislodgeable residue.

    View details for DOI 10.1021/es0351342

    View details for Web of Science ID 000224234100055

    View details for PubMedID 15506225

  • Arsenite retention mechanisms within estuarine sediments of Pescadero, CA ENVIRONMENTAL SCIENCE & TECHNOLOGY Bostick, B. C., Chen, C., Fendorf, S. 2004; 38 (12): 3299-3304

    Abstract

    Arsenic, a toxic metalloid, is commonly associated with sulfide minerals in anoxic sediments. Here we characterize arsenic(III) retention on sediments from a sulfidic estuarine marsh using a series of sorption experiments, and probe the structure of retained arsenite with X-ray absorption spectroscopy. Although the extent of sorption varied with sampling locations, several adsorption characteristics were apparent. A fraction of arsenite adsorbed over the entire pH range examined, although it was most extensive at pH greater than 7, and conformed to a Langmuir isotherm. Iron sulfide phases were responsible for As partitioning in these sediments. Initially, an FeAsS-like precipitate formed with a structure similar to those reported for As(III) sorbed on iron sulfides, a complex that is highly reactive. Following reaction for 21 d, much of the FeAsS-like precipitate was converted to As2S3. A drop in the redox potential accompanied this conversion, suggesting that the evolution of sulfide and other reduced species stabilizes bound arsenic. Processes discerned in this study reveal the importance of sulfide minerals in As sequestration within anoxic environments.

    View details for DOI 10.1021/es035006d

    View details for Web of Science ID 000222051400023

    View details for PubMedID 15260327

  • Chrominium geochemistry of serpentine soils INTERNATIONAL GEOLOGY REVIEW Oze, C., Fendorf, S., Bird, D. K., Coleman, R. G. 2004; 46 (2): 97-126
  • Chromium geochemistry in serpentinized ultramafic rocks and serpentine soils from the Franciscan Complex of California AMERICAN JOURNAL OF SCIENCE Oze, C., Fendorf, S., Bird, D. K., Coleman, R. G. 2004; 304 (1): 67-101
  • Enrichment of Mo in hydrothermal Mn precipitates: possible Mo sources, formation process and phase associations CHEMICAL GEOLOGY Kuhn, T., Bostick, B. C., Koschinsky, A., Halbach, P., Fendorf, S. 2003; 199 (1-2): 29-43
  • Secondary mineralization pathways induced by dissimilatory iron reduction of ferrihydrite under advective flow GEOCHIMICA ET COSMOCHIMICA ACTA Hansel, C. M., Benner, S. G., Neiss, J., Dohnalkova, A., Kukkadapu, R. K., Fendorf, S. 2003; 67 (16): 2977-2992
  • Kinetics and structural constraints of chromate reduction by green rusts ENVIRONMENTAL SCIENCE & TECHNOLOGY Bond, D. L., Fendorf, S. 2003; 37 (12): 2750-2757

    Abstract

    Green rusts, ferrous-ferric iron oxides, occur in many anaerobic soils and sediments and are highly reactive, making them important phases impacting the fate and transport of environmental contaminants. Despite their potential importance in environmental settings, reactions involving green rusts remain rather poorly described. Chromate is a widespread contaminant having deleterious impacts on plant and animal health; its fate may in part be controlled by green rust. Here we examine chromate reduction by a series of green rust phases and resolve the reaction kinetics at pH 7. The overall kinetics of the reactions are well described by the expression d[Cr(VI)]/dt = -k[Cr(VI)][GR], and this model was successfully used to predict rates of reaction at varying chromium concentrations. The rates of reduction are controlled by the concentration of ferrous iron, surface area, and chemical structure of the green rust including layer spacing. On a mass basis, green rust (GR) chloride is the most rapid reductant of Cr(VI) followed by GRCO3 and GRSO4, with pseudo-first-order rate coefficients (k(obs)) (with respect to Cr(VI) concentration) ranging from 1.22 x 10(-3) to 3.7 x 10(-2) s(-1). Chromium(III)-substituted magnetite and lepidocrocite were identified as the major oxidation products. The nature of the oxidation products appears to be independent of the anionic class of green rust, but their respective concentrations display a dependence on the initial GR. The mole fraction of Fe(III) in the Cr(x),Fe(1-x)(OH)3 x nH2O reaction product ranged from 17% to 68%, leading to a highly stabilized (low solubility) phase.

    View details for DOI 10.1021/es026341p

    View details for Web of Science ID 000183504900018

    View details for PubMedID 12854715

  • Inhihition of bacterial U(VI) reduction by calcium ENVIRONMENTAL SCIENCE & TECHNOLOGY Brooks, S. C., Fredrickson, J. K., Carroll, S. L., Kennedy, D. W., Zachara, J. M., Plymale, A. E., Kelly, S. D., Kemner, K. M., Fendorf, S. 2003; 37 (9): 1850-1858

    Abstract

    The rapid kinetics of bacterial U(VI) reduction and low solubility of uraninite (UO2,cr) make this process an attractive option for removing uranium from groundwater. Nevertheless, conditions that may promote or inhibit U(VI) reduction are not well-defined. Recent descriptions of Ca-UO2-CO3 complexes indicate that these species may dominate the aqueous speciation of U(VI) in many environments. We monitored the bacterial reduction of U(VI) in bicarbonate-buffered solution in the presence and absence of Ca. XAFS measurements confirmed the presence of a Ca-U(VI)-C03 complex in the initial solutions containing calcium. Calcium, at millimolar concentrations (0.45-5 mM), caused a significant decrease in the rate and extent of bacterial U(VI) reduction. Both facultative (Shewanella putrefaciens strain CN32) and obligate (Desulfovibrio desulfuricans, Geobacter sulfurreducens) anaerobic bacteria were affected by the presence of calcium. Reduction of U(VI) ceased when the calculated system Eh reached -0.046 +/- 0.001 V, based on the Ca2UO2(CO3)3 --> UO2,cr couple. The results are consistent with the hypothesis that U is a less energetically favorable electron acceptor when the Ca-UO2-CO3 complexes are present. The results do not support Ca inhibition caused by direct interactions with the cells or with the electron donor as the reduction of fumarate or Tc(VII)O4- under identical conditions was unaffected by the presence of Ca.

    View details for DOI 10.1021/es0210042

    View details for Web of Science ID 000182635200039

    View details for PubMedID 12775057

  • Structural and compositional evolution of Cr/Fe solids after indirect chromate reduction by dissimilatory iron-reducing bacteria GEOCHIMICA ET COSMOCHIMICA ACTA Hansel, C. M., Wielinga, B. W., Fendorf, S. R. 2003; 67 (3): 401-412
  • Differential adsorption of molybdate and tetrathiomolybdate on pyrite (FeS2) ENVIRONMENTAL SCIENCE & TECHNOLOGY Bostick, B. C., Fendorf, S., Helz, G. R. 2003; 37 (2): 285-291

    Abstract

    Molybdenum is a nutrient important for a variety of biological functions, most notably nitrogen fixation. Molybdenum availability is limited through sorption reactions, particularly in environments rich in sulfide minerals. This study examines the sorption of two major molybdenum species, molybdate (MoO4(2-)) and tetrathiomolybdate (MoS4(2-)), on synthetic pyrite (FeS2) as a function of solution composition. Both MoO4(2-) and MoS4(2-) partitioned strongly on FeS2 under a range of conditions and ionic strengths. Molybdate and tetrathiomolybdate adsorption obeyed a Langmuir isotherm with a calculated site density between 2 and 3 sites/nm2 under acidic and circumneutral conditions, which decreased to less than 1 site/ nm2 at pH 9. Although both MoO4(2-) and MoS4(2-) adsorbed most strongly under moderately acidic conditions, MoO4(2-) readily desorbed while MoS4(2-) remained adsorbed even at high pH. The reversibility of MoO4(2-) adsorption suggests the formation of labile surface complexes while MoS4(2-) likely forms strong inner-sphere complexes. X-ray absorption spectroscopy was used to determine the structure of the surface complexes. Molybdate formed bidentate, mononuclear complexes on FeS2. The Mo-S and Mo-Fe distances for tetrathiomolybdate on pyrite are consistent with the formation of Mo-Fe-S cubane-type clusters. The high affinity of MoS4(2-) for FeS2, as well as its resistance to desorption, supports the hypothesis that thiomolybdate species are the reactive Mo constituents in reduced sediments and may control Mo enrichment in anoxic marine environments.

    View details for DOI 10.1021/es027487

    View details for Web of Science ID 000180501500012

    View details for PubMedID 12564899

  • Effects of contaminant concentration, aging, and soil properties on the bioaccessibility of Cr(III) and Cr(VI) in soil SOIL & SEDIMENT CONTAMINATION Stewart, M. A., Jardine, P. M., Brandt, C. C., Barnett, M. O., Fendorf, S. E., McKay, L. D., Mehlhorn, T. L., Paul, K. 2003; 12 (1): 1-21
  • Arsenite adsorption on galena (PbS) and sphalerite (ZnS) Geochimica et Cosmochimica Acta Bostick, B. C., Fendorf, S., Manning, B. A. 2003; 37: 285-291
  • Arsenic(III) complexation and oxidation reactions on soil BIOGEOCHEMISTRY OF ENVIRONMENTALLY IMPORTANT TRACE ELEMENTS Manning, B. A., Fendorf, S. E., Suarez, D. L. 2003; 835: 57-69
  • Seasonal transformations of manganese in a palustrine emergent wetland SOIL SCIENCE SOCIETY OF AMERICA JOURNAL La Force, M. J., Hansel, C. M., Fendorf, S. 2002; 66 (4): 1377-1389
  • Spatial and temporal association of As and Fe species on aquatic plant roots ENVIRONMENTAL SCIENCE & TECHNOLOGY Hansel, C. M., La Force, M. J., Fendorf, S., Sutton, S. 2002; 36 (9): 1988-1994

    Abstract

    The formation of an Fe(III) precipitate (plaque) on the surface of aquatic plant roots may provide a means of attenuation and external exclusion of metals. Presently, the mechanisms of metal(loid) sequestration at the root surface are unresolved. Accordingly, we investigated the mechanisms of Fe and As attenuation and association on the roots of two common aquatic plant species, Phalaris arundinacea (reed canarygrass) and Typha latifolia (cattail) using X-ray absorption spectroscopy and X-ray fluorescence microtomography. Iron plaque of both P. arundinacea and T. latifolia consist predominantly of hydrated iron oxides (ferrihydrite) with lesser amounts of goethite and minor levels of siderite. Typha latifolia, however, differs from P. arundinacea by having a significant contribution from lepidocrocite as well as a greater proportion of crystalline minerals. Coexistence of goethite and lepidocrocite suggests the presence of chemically diverse microenvironments at the root surface. Arsenic exists as a combination of two sorbed As species, being comprised predominantly of arsenate- (approximately 82%) with lesser amounts (approximately 18%) of As(III)-iron (hydr)oxide complexes. Furthermore, both spatial and temporal correlations between As and Fe on the root surfaces were observed. While the iron (hydr)oxide deposits form a continuous surficial rind around the root, As exists in isolated regions on the exterior and interior of the root. Root surface-associated As generally corresponds to regions of enhanced Fe levels and may therefore occur as a direct consequence of Fe phase heterogeneity and preferential As sorption reactions.

    View details for DOI 10.1021/es015647d

    View details for Web of Science ID 000175311900022

    View details for PubMedID 12026982

  • Reductive dissolution and biomineralization of iron hydroxide under dynamic flow conditions ENVIRONMENTAL SCIENCE & TECHNOLOGY Benner, S. G., Hansel, C. M., Wielinga, B. W., Barber, T. M., Fendorf, S. 2002; 36 (8): 1705-1711

    Abstract

    Iron cycling and the associated changes in solid phase have dramatic implications for trace element mobility and bioavailability. Here we explore the formation of secondary iron phases during microbially mediated reductive dissolution of ferrihydrite-coated sand under dynamic flow conditions. An initial period (10 d) of rapid reduction, indicated by consumption of lactate and production of acetate and Fe-(II) to the pore water in association with a darkening of the column material, is followed by much lower rate of reduction to the termination of the experiment after 48 d. Although some Fe (<25%) is lost to the effluent pore water, the majority remains within the column as ferrihydrite (20-70%) and the secondary mineral phases magnetite (0-70%) and goethite (0-25%). Ferrihydrite converts to goethite in the influent end of the column where dissolved Fe(II) concentrations are low and converts to magnetite toward the effluent end where Fe(III) concentrations are elevated. A decline in the rate of Fe(II) production occurs concurrent with the formation of goethite and magnetite; at the termination of the experiment, the rate of reduction is <5% the initial rate. Despite the dramatic decrease in the rate of reduction, greater than 80% of the residual Fe remains in the ferric state. These results highlight the importance of coupled flow and water chemistry in controlling the rate and solid-phase products of iron (hydr)oxide reduction.

    View details for DOI 10.1021/es0156441

    View details for Web of Science ID 000174976300010

    View details for PubMedID 11993867

  • Arsenic(III) oxidation and arsenic(V) adsorption reactions on synthetic birnessite ENVIRONMENTAL SCIENCE & TECHNOLOGY Manning, B. A., Fendorf, S. E., Bostick, B., Suarez, D. L. 2002; 36 (5): 976-981

    Abstract

    The oxidation of arsenite (As(III)) by manganese oxide is an important reaction in both the natural cycling of As and the development of remediation technology for lowering the concentration of dissolved As(III) in drinking water. This study used both a conventional stirred reaction apparatus and extended X-ray absorption fine structure (EXAFS) spectroscopy to investigate the reactions of As(III) and As(V) with synthetic birnessite (MnO2). Stirred reactor experiments indicate that As(III) is oxidized by MnO2 followed by the adsorption of the As(V) reaction product on the MnO2 solid phase. The As(V)-Mn interatomic distance determined by EXAFS analysis for both As(III)- and As(V)-treated MnO2 was 3.22 A, giving evidence for the formation of As(V) adsorption complexes on MnO2 crystallite surfaces. The most likely As(V)-MnO2 complex is a bidentate binuclear corner sharing (bridged) complex occurring at MnO2 crystallite edges and interlayer domains. In the As(III)-treated MnO2 systems, reductive dissolution of the MnO2 solid during the oxidation of As(III) caused an increase in the adsorption of As(V) when compared with As(V)-treated MnO2. This suggested that As(III) oxidation caused a surface alteration, creating fresh reaction sites for As(V) on MnO2 surfaces.

    View details for DOI 10.1021/es0110170

    View details for Web of Science ID 000174136400038

    View details for PubMedID 11918029

  • Uranyl surface complexes formed on subsurface media from DOE facilities SOIL SCIENCE SOCIETY OF AMERICA JOURNAL Bostick, B. C., Fendorf, S., Barnett, M. O., Jardine, P. M., Brooks, S. C. 2002; 66 (1): 99-108
  • Characterization of Fe plaque and associated metals on the roots of mine-waste impacted aquatic plants ENVIRONMENTAL SCIENCE & TECHNOLOGY Hansel, C. M., Fendorf, S., Sutton, S., Newville, M. 2001; 35 (19): 3863-3868

    Abstract

    Iron plaque on aquatic plant roots are ubiquitous and sequester metals in wetland soils; however, the mechanisms of metal sequestration are unresolved. Thus, characterizing the Fe plaque and associated metals will aid in understanding and predicting metal cycling in wetland ecosystems. Accordingly, microscopic and spectroscopic techniques were utilized to identify the spatial distributions, associations, and chemical environments of Fe, Mn, Pb, and Zn on the roots of a common, indigenous wetland plant (Phalaris arundinacea). Iron forms a continuous precipitate on the root surface, which is composed dominantly of ferrihydrite (ca. 63%) with lesser amounts of goethite (32%) and minor levels of siderite (5%). Although Pb is juxtaposed with Fe on the root surface, it is complexed to organic functional groups, consistent with those of bacterial biofilms. In contrast, Mn and Zn exist as discrete, isolated mixed-metal carbonate (rhodochrosite/hydrozincite) nodules on the root surface. Accordingly, the soil-root interface appears to be a complex biochemical environment, containing both reduced and oxidized mineral species, as well as bacterial-induced organic-metal complexes. As such, hydrated iron oxides, bacterial biofilms, and metal carbonates will influence the availability and mobility of metals within the rhizosphere of aquatic plants.

    View details for DOI 10.1021/es0105459

    View details for Web of Science ID 000171352500020

    View details for PubMedID 11642445

  • Seasonal fluctuations in zinc speciation within a contaminated wetland ENVIRONMENTAL SCIENCE & TECHNOLOGY Bostick, B. C., Hansel, C. M., La Force, M. J., Fendorf, S. 2001; 35 (19): 3823-3829

    Abstract

    The cycling of common sorbents such as metal (hydr)- oxides, carbonates, and sulfides in redox-active environments influences the partitioning of associated trace elements such as zinc. Consequently, fluctuations in redox status may in part determine the availability and mobility of Zn and other trace elements. This research examines changes in Zn speciation in a contaminated wetland soil that undergoes seasonal flooding. X-ray absorption spectroscopy (XAS) was employed to identify and quantify Zn species from soil cores collected over a 1-year cycle as a function of water depth, location, and soil depth. Zinc associated with (hydr)oxide phases in dry, oxidized soils and with sulfides and carbonates in flooded systems. An increase in water level was accompanied by a reversible change in Zn fractionation toward ZnS and ZnC03. However, a small, recalcitrant fraction of Zn associated with (hydr)oxides remained even when the soils were exposed to highly reducing conditions. Water depth and redox potential were the most important factors in determining Zn speciation, although spatial variation was also important. These data indicate that zinc sorption is a dynamic process influenced by environmental changes.

    View details for DOI 10.1021/es010549d

    View details for Web of Science ID 000171352500014

    View details for PubMedID 11642439

  • Co(II0I)EDTA(-) reduction by Desulfovibrio vulgaris and propagation of reactions involving dissolved sulfide and polysulfides ENVIRONMENTAL SCIENCE & TECHNOLOGY Blessing, T. C., Wielinga, B. W., Morra, M. J., Fendorf, S. 2001; 35 (8): 1599-1603

    Abstract

    The migration of 60Co, dominantly via transport of Co-EDTA complexes, into surface water and groundwater is a recognized concern at many nuclear production and storage sites. Reduction of CoIIIEDTA- to CoIIEDTA2- should decrease the mobility of 60Co in natural environments by stimulating ligand displacement with Fe(III) or Al(III) or by precipitation of CoSx in sulfidic environments. In this study, we examine direct (enzymatic) and indirect (metabolite) reduction processes of CoIIIEDTA- by the sulfate-reducing bacterium Desulfovibrio vulgaris. D. vulgaris reduces CoIIIEDTA- to CoIIEDTA2-, but growth using it as a terminal electron acceptor was not demonstrated. Rather than acting as a competing electron acceptor and limiting cobalt reduction, introducing sulfate with D. vulgaris enhances the reduction of CoIIIEDTA- as a result of sulfide production. Sulfide reduces CoIIIEDTA- in a pathway involving polysulfide formation and leads to a CoS precipitate. Thus, both direct and indirect (i.e., through the production of sulfide) microbial reduction pathways of CoIIIEDTA- may help to retard its migration within soils and waters.

    View details for Web of Science ID 000168099000007

    View details for PubMedID 11329708

  • Iron promoted reduction of chromate by dissimilatory iron-deducing bacteria ENVIRONMENTAL SCIENCE & TECHNOLOGY Wielinga, B., Mizuba, M. M., Hansel, C. M., Fendorf, S. 2001; 35 (3): 522-527

    Abstract

    Chromate is a priority pollutant within the U.S. and many other countries, the hazard of which can be mitigated by reduction to the trivalent form of chromium. Here we elucidate the reduction of Cr(VI) to Cr(III) via a closely coupled, biotic-abiotic reductive pathway under iron-reducing conditions. Injection of chromate into stirred-flow reactors containing Shewanella alga strain BrY and iron (hydr)oxides of varying stabilities results in complete reduction to Cr(III). The maximum sustainable Cr(VI) reduction rate was 5.5 micrograms CrVI.mg-cell-1.h-1 within ferric (hydr)oxide suspensions (surface area 10 m2). In iron limited systems (having HEPES as a buffer), iron was cycled suggesting it acts in a catalytic-type manner for the bacterial reduction of Cr(VI). BrY also reduced Cr(VI) directly; however, the rate of direct (enzymatic) reduction is considerably slower than by Fe(II)(aq) and is inhibited within 20 h due to chromate toxicity. Thus, dissimilatory iron reduction may provide a primary pathway for the sequestration and detoxification of chromate in anaerobic soils and water.

    View details for Web of Science ID 000166727700024

    View details for PubMedID 11351723

  • Kinetics of arsenate reduction by dissolved sulfide ENVIRONMENTAL SCIENCE & TECHNOLOGY Rochette, E. A., Bostick, B. C., Li, G. C., Fendorf, S. 2000; 34 (22): 4714-4720
  • Multispecies transport of metal-EDTA complexes and chromate through undisturbed columns of weathered fractured saprolite JOURNAL OF CONTAMINANT HYDROLOGY Mayes, M. A., Jardine, P. M., Larsen, I. L., Brooks, S. C., Fendorf, S. E. 2000; 45 (3-4): 243-265
  • Arsenic speciation, seasonal transformations, and co-distribution with iron in a mine waste-influenced palustrine emergent wetland ENVIRONMENTAL SCIENCE & TECHNOLOGY La Force, M. J., Hansel, C. M., Fendorf, S. 2000; 34 (18): 3937-3943

    View details for DOI 10.1021/es0010150

    View details for Web of Science ID 000089315600018

  • Solid-phase iron characterization during common selective sequential extractions SOIL SCIENCE SOCIETY OF AMERICA JOURNAL La Force, M. J., Fendorf, S. 2000; 64 (5): 1608-1615
  • Chromium transformations in natural environments: The role of biological and abiological. processes in chromium(VI) reduction INTERNATIONAL GEOLOGY REVIEW Fendorf, S., Wielinga, B. W., Hansel, C. M. 2000; 42 (8): 691-701
  • Inhibition of bacterially promoted uranium reduction: Ferric (hydr)oxides as competitive electron acceptors ENVIRONMENTAL SCIENCE & TECHNOLOGY Wielinga, B., Bostick, B., Hansel, C. M., Rosenzweig, R. F., Fendorf, S. 2000; 34 (11): 2190-2195
  • Purification to homogeneity and characterization of a novel Pseudomonas putida chromate reductase APPLIED AND ENVIRONMENTAL MICROBIOLOGY Park, C. H., Keyhan, M., Wielinga, B., Fendorf, S., Matin, A. 2000; 66 (5): 1788-1795

    Abstract

    Cr(VI) (chromate) is a widespread environmental contaminant. Bacterial chromate reductases can convert soluble and toxic chromate to the insoluble and less toxic Cr(III). Bioremediation can therefore be effective in removing chromate from the environment, especially if the bacterial propensity for such removal is enhanced by genetic and biochemical engineering. To clone the chromate reductase-encoding gene, we purified to homogeneity (>600-fold purification) and characterized a novel soluble chromate reductase from Pseudomonas putida, using ammonium sulfate precipitation (55 to 70%), anion-exchange chromatography (DEAE Sepharose CL-6B), chromatofocusing (Polybuffer exchanger 94), and gel filtration (Superose 12 HR 10/30). The enzyme activity was dependent on NADH or NADPH; the temperature and pH optima for chromate reduction were 80 degrees C and 5, respectively; and the K(m) was 374 microM, with a V(max) of 1.72 micromol/min/mg of protein. Sulfate inhibited the enzyme activity noncompetitively. The reductase activity remained virtually unaltered after 30 min of exposure to 50 degrees C; even exposure to higher temperatures did not immediately inactivate the enzyme. X-ray absorption near-edge-structure spectra showed quantitative conversion of chromate to Cr(III) during the enzyme reaction.

    View details for Web of Science ID 000086805500003

    View details for PubMedID 10788340

  • Influence of cadmium sorption on FeS2 oxidation ENVIRONMENTAL SCIENCE & TECHNOLOGY Bostick, B. C., Fendorf, S., Bowie, B. T., Griffiths, P. R. 2000; 34 (8): 1494-1499
  • Constructing simple wetland sampling devices SOIL SCIENCE SOCIETY OF AMERICA JOURNAL LaForce, M. J., Hansel, C. M., Fendorf, S. 2000; 64 (2): 809-811
  • Disulfide disproportionation and CdS formation upon cadmium sorption on FeS2 GEOCHIMICA ET COSMOCHIMICA ACTA Bostick, B. C., Fendorf, S., Fendorf, M. 2000; 64 (2): 247-255
  • Evidence for microbial Fe(III) reduction in anoxic, mining-impacted lake sediments (Lake Coeur d'Alene, USA) Applied and Environmental Microbiology Cummings, D. E., March, A. W., Bostick, B. C., Spring, S., Caccavo, F., Jr., S. Fendorf, Rosenzweig, R. F. 2000; 66: 154-162
  • Pyrolusite surface transformations measured in real-time during the reactive transport of Co(II)EDTA(2-) GEOCHIMICA ET COSMOCHIMICA ACTA Fendorf, S., Jardine, P. M., Patterson, R. R., TAYLOR, D. L., Brooks, S. C. 1999; 63 (19-20): 3049-3057
  • Fate and transport of hexavalent chromium in undisturbed heterogeneous soil ENVIRONMENTAL SCIENCE & TECHNOLOGY Jardine, P. M., Fendorf, S. E., Mayes, M. A., Larsen, I. L., Brooks, S. C., Bailey, W. B. 1999; 33 (17): 2939-2944
  • Arsenic sorption in phosphate-amended soils during flooding and subsequent aeration SOIL SCIENCE SOCIETY OF AMERICA JOURNAL Reynolds, J. G., Naylor, D. V., Fendorf, S. E. 1999; 63 (5): 1149-1156
  • Redistribution of trace elements from contaminated sediments of Lake Coeur d'Alene during oxygenation JOURNAL OF ENVIRONMENTAL QUALITY La Force, M. J., Fendorf, S., Li, G. C., Rosenzweig, R. F. 1999; 28 (4): 1195-1200
  • Arsenic mobilization by the dissimilatory Fe(III) reducing bacterium Shewanella alga BrY Environmental Science & Technology Cummings, D., Caccavo, F., Fendorf, S., Rosenzweig, R. F. 1999; 33: 723-729
  • Phase associations and mobilization of iron and trace metals in sediments of Lake Coeur d'Alene, Idaho Environmental Science & Technology Harrington, J. M., Rosenzweig, R. F., Rember, W. C., Fendorf, S. E. 1998; 32: 650-656
  • Reaction sequence of nickelsorption on kaolinite Soil Science Society of America Journal Eick, M. J., Fendorf, S. E. 1998; 62: 1257-1267
  • Surface structures and stability of arsenic(III) on goethite: Spectroscopic evidence for inner-sphere complexes Environmental Science & Technology Manning, B. A., Fendorf, S. E., Goldberg, S. 1998; 32: 2383-2388
  • Alteration of arsenic sorption in flooded-dried soils Soil Science Society of America Journal McGeehan, S. L., Fendorf, S. E., Naylor, D. V. 1998; 62: 828-833
  • Biotic generation of arsenic(III) in metal contaminated lake sediments Environmental Science & Technology Harrington, J. M., Fendorf, S. E., Rosenzwieg, R. F. 1998; 32: 2425-2430
  • Mobility of trace-element contaminants upon flooding of the Coeur d'Alene River Journal of Environmental Quality LaForce, M. J., Fendorf, S. E., Li, G. C., Schneider, M., Rosenzweig, R. F. 1998; 27: 318-328
  • Stability of arsenate minerals in soils under biotically-generated reducing conditions Soil Science Society of America Journal Rochette, E. A., Li, G. C., Fendorf, S. E. 1998; 62: 1530-1537
  • Reduction of hexavalent chromium by amorphous iron sulfide ENVIRONMENTAL SCIENCE & TECHNOLOGY Patterson, R. R., Fendorf, S., Fendorf, M. 1997; 31 (7): 2039-2044
  • Sorption mechanisms of lanthanum on oxide minerals CLAYS AND CLAY MINERALS Fendorf, S., Fendorf, M. 1996; 44 (2): 220-227
  • Mechanism of aluminum sorption on birnessite: Influences on chromium (III) oxidation 15TH WORLD CONGRESS OF SOIL SCIENCE, VOL 3A, TRANSACTIONS Fendorf, S. E., Sparks, D. L., Fendorf, M. 1994: 129-130

Books and Book Chapters


  • Arsenic Chemistry in Soils and Sediments Synchrotron-Based Techniques in Soils and Sediments. Elsevier Publishing Fendorf, S., Nico, P. S., Kocar, B. D., Masue, Y., Tufano, K. J. edited by Singh, B., Grafe, M. 2010: 357-378
  • Biogeochemical uranium redox transformations: Potential oxidants of uraninite Adsorption to Geomedia Ginder-Vogel, M., Fendorf, S. edited by Barnett, M. A., Kent, D. B. Academic Press, NY. 2007: 293-321
  • Biogeochemical processes controlling the cycling of arsenic in soils and sediments Biophysico-Chemical Processes of Heavy Metals and Metalloids in Soil Environments. IUPAC Division VI-Chemistry and the Environment Fendorf, S. M., Herbel, J., Tufano, K. J., Kocar, B. edited by Violante, A., Huang, P. M., Gadd, G. John Wiley & Sons, Chichester, England. 2007: 313-338
  • Phosphate interactions with iron (hydr)oxides: Mineralization pathways and phosphorus retention upon bioreduction Adsorption to Geomedia Borch, T., Fendorf, S. edited by Barnett, M. A., Kent, D. B. Academic Press, NY . 2007: 322-348
  • Soil chemistry and mineralogy: Kinetics of redox reactions Encyclopedia of Soils in the Environment Nico, P. S., Fendorf, S. edited by Hillel, D. Academic Press. 2004
  • Arsenic (V/III) cycling in soils and natural waters: Chemical and microbiological processes Environmental Chemistry of Arsenic Inskeep, , W. P., McDermott, T. R., Fendorf, S. E. edited by Frankenberger, Jr., W. T. Spinger-Verlag. 2002: 183-215
  • Soil Geochemical Processes of Radionuclides Soil Sci. Soc. Am. Special Publication Fendorf, S., Wielinga, B. W., Hansel, C. M. edited by Zhang, P. C., Brady, P. Soil Science Society of America. 2002
  • Ecosystem dynamics of zinc and manganese within a mine-waste impacted wetland Crerar Volume Hansel, C. M., LaForce, M. J., Sutton, S. E., Fendorf, S. edited by Wood, S., Hellmann, R. Geochemical Society of America. 2001
  • Fundamental aspects and applications of x-ray absorption spectroscopy in clay and soil science Applications of synchrotron radiation in clay science Fendorf, S. E. edited by Schulze, D. G., Bertsch, P. M. Clay Mineral Society, Ottawa, Canada. 1999: 31-74
  • Kinetics and mechanisms of reactions at the mineral/water interface American Chemical Society Special Publication Fendorf, S. E., Jardine, P. M., Taylor, D. L., Brooks, S. C., Rochette, E. A. edited by Sparks, D. L., Grundl, T. American Chemical Society. 1998

Conference Proceedings