Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate
Abstract
Iron oxides are ubiquitous in soils and sediments and play a critical role in the geochemical distribution of trace elements and heavy metals via adsorption and coprecipitation. The presence of organic acids may potentially alter how metals associate with iron oxide minerals through a series of cooperative or competitive processes: solution complexation, ternary surface complexation, and surface site competition. The macroscopic and molecular-scale effects of these processes were investigated for Ni adsorption to hematite and goethite at pH 7 in the presence of oxalate. The addition of this organic acid suppresses Ni uptake on both minerals. Aqueous speciation suggests that this is dominantly the result of oxalate complexing and solubilizing Ni. Comparison of the Ni surface coverage to the concentration of free (uncomplexed) Ni2+ in solution suggests that the oxalate also alters Ni adsorption affinity. EXAFS and ATR-FTIR spectroscopies indicate that these changes in binding affinity are due to the formation of Ni–oxalate ternary surface complexes. Here, these observations demonstrate that competition between dissolved oxalate and the mineral surface for Ni overwhelms the enhancement in adsorption associated with ternary complexation. Oxalate thus largely enhances Ni mobility, thereby increasing micronutrient bioavailability and inhibiting contaminant sequestration.
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Science Foundation (NSF)
- OSTI Identifier:
- 1379430
- Grant/Contract Number:
- DGE-1745038; AC02-06CH11357; ECS-0335765
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Environmental Science and Technology
- Additional Journal Information:
- Journal Volume: 51; Journal Issue: 17; Journal ID: ISSN 0013-936X
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 54 ENVIRONMENTAL SCIENCES; anions; complexation; hematite; adsorption; minerals
Citation Formats
Flynn, Elaine D., and Catalano, Jeffrey G. Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate. United States: N. p., 2017.
Web. doi:10.1021/acs.est.7b02657.
Flynn, Elaine D., & Catalano, Jeffrey G. Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate. United States. https://doi.org/10.1021/acs.est.7b02657
Flynn, Elaine D., and Catalano, Jeffrey G. Mon .
"Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate". United States. https://doi.org/10.1021/acs.est.7b02657. https://www.osti.gov/servlets/purl/1379430.
@article{osti_1379430,
title = {Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate},
author = {Flynn, Elaine D. and Catalano, Jeffrey G.},
abstractNote = {Iron oxides are ubiquitous in soils and sediments and play a critical role in the geochemical distribution of trace elements and heavy metals via adsorption and coprecipitation. The presence of organic acids may potentially alter how metals associate with iron oxide minerals through a series of cooperative or competitive processes: solution complexation, ternary surface complexation, and surface site competition. The macroscopic and molecular-scale effects of these processes were investigated for Ni adsorption to hematite and goethite at pH 7 in the presence of oxalate. The addition of this organic acid suppresses Ni uptake on both minerals. Aqueous speciation suggests that this is dominantly the result of oxalate complexing and solubilizing Ni. Comparison of the Ni surface coverage to the concentration of free (uncomplexed) Ni2+ in solution suggests that the oxalate also alters Ni adsorption affinity. EXAFS and ATR-FTIR spectroscopies indicate that these changes in binding affinity are due to the formation of Ni–oxalate ternary surface complexes. Here, these observations demonstrate that competition between dissolved oxalate and the mineral surface for Ni overwhelms the enhancement in adsorption associated with ternary complexation. Oxalate thus largely enhances Ni mobility, thereby increasing micronutrient bioavailability and inhibiting contaminant sequestration.},
doi = {10.1021/acs.est.7b02657},
journal = {Environmental Science and Technology},
number = 17,
volume = 51,
place = {United States},
year = {Mon Jul 31 00:00:00 EDT 2017},
month = {Mon Jul 31 00:00:00 EDT 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 38 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Iron Oxides in the Laboratary
book, April 2000
- Schwertmann, U.; Cornell, R. M.
- WILEY-VCH Verlag GmbH
Composition and structure of nanocrystalline Fe and Mn oxide cave deposits: Implications for trace element mobility in karst systems
journal, May 2011
- Frierdich, Andrew J.; Hasenmueller, Elizabeth A.; Catalano, Jeffrey G.
- Chemical Geology, Vol. 284, Issue 1-2
Nanoparticulate Iron Oxide Minerals in Soils and Sediments: Unique Properties and Contaminant Scavenging Mechanisms
journal, October 2005
- Waychunas, Glenn A.; Kim, Christopher S.; Banfield, Jillian F.
- Journal of Nanoparticle Research, Vol. 7, Issue 4-5
Sorption of Trace Elements on Mineral Surfaces: Modern Perspectives from Spectroscopic Studies, and Comments on Sorption in the Marine Environment
journal, November 2001
- Brown, Gordon E.; Parks, George A.
- International Geology Review, Vol. 43, Issue 11
Molecular-Scale Speciation of Zn and Ni in Soil Ferromanganese Nodules from Loess Soils of the Mississippi Basin
journal, January 2003
- Manceau, Alain; Tamura, Nobumichi; Celestre, Richard S.
- Environmental Science & Technology, Vol. 37, Issue 1
Annual accretion of Fe−Mn-oxides and certain associated metals in a stream environment
journal, January 1980
- Carpenter, R. H.; Hayes, W. B.
- Chemical Geology, Vol. 29, Issue 1-4
Properties and distribution of iron oxides and their association with minor elements in the soils of south-western Australia
journal, March 1992
- Singh, B.; Gilkes, R. J.
- Journal of Soil Science, Vol. 43, Issue 1
Environmentally important, poorly crystalline Fe/Mn hydrous oxides: Ferrihydrite and a possibly new vernadite-like mineral from the Clark Fork River Superfund Complex
journal, April 2005
- Hochella, M. F.
- American Mineralogist, Vol. 90, Issue 4
Spectroscopic Evidence for Ni(II) Surface Speciation at the Iron Oxyhydroxides−Water Interface
journal, February 2008
- Arai, Yuji
- Environmental Science & Technology, Vol. 42, Issue 4
Adsorption of Cu, Cd, and Ni on Goethite in the Presence of Natural Groundwater Ligands
journal, February 2002
- Buerge-Weirich, Diane; Hari, Renata; Xue, Hanbin
- Environmental Science & Technology, Vol. 36, Issue 3
Adsorption of Copper, Nickel, and Cadmium on Goethite in the Presence of Organic Ligands
journal, June 2003
- Buerge-Weirich, Diane; Behra, Philippe; Sigg, Laura
- Aquatic Geochemistry, Vol. 9, Issue 2
Nonreversible Adsorption of Divalent Metal Ions (MnII, CoII, NiII, CuII, and PbII) onto Goethite: Effects of Acidification, FeII Addition, and Picolinic Acid Addition
journal, September 1995
- Coughlin, Barbara R.; Stone, Alan T.
- Environmental Science & Technology, Vol. 29, Issue 9
Ni and Zn Sorption to Amorphous versus Crystalline Iron Oxides: Macroscopic Studies
journal, December 2001
- Trivedi, Paras; Axe, Lisa
- Journal of Colloid and Interface Science, Vol. 244, Issue 2
Trace Metal Requirements for Microbial Enzymes Involved in the Production and Consumption of Methane and Nitrous Oxide
journal, January 2012
- Glass, Jennifer B.; Orphan, Victoria J.
- Frontiers in Microbiology, Vol. 3
Organic acids in the rhizosphere – a critical review
journal, August 1998
- Jones, David L.
- Plant and Soil, Vol. 205, Issue 1, p. 25-44
Low-Molecular-Weight Organic Acids in Selected Forest Soils of the Southeastern USA
journal, July 1990
- Fox, T. R.; Comerford, N. B.
- Soil Science Society of America Journal, Vol. 54, Issue 4
Dissolved components in precipitation water percolated through forest litter: Dissolved components in forest litter percolates
journal, December 2000
- Hongve, D.; Van Hees, P. A. W.; Lundström, U. S.
- European Journal of Soil Science, Vol. 51, Issue 4
Organics in Water-Rock Interactions
journal, January 2009
- Ganor, J.; Reznik, I. J.; Rosenberg, Y. O.
- Reviews in Mineralogy and Geochemistry, Vol. 70, Issue 1
Microbial production of organic acids in aquitard sediments and its role in aquifer geochemistry
journal, January 1991
- McMahon, Peter B.; Chapelle, Francis H.
- Nature, Vol. 349, Issue 6306
Adsorption of Small Weak Organic Acids on Goethite: Modeling of Mechanisms
journal, November 1997
- Filius, Jeroen D.; Hiemstra, Tjisse; Van Riemsdijk, Willem H.
- Journal of Colloid and Interface Science, Vol. 195, Issue 2
Interaction of Zn(II) with Hematite Nanoparticles and Microparticles: Part 2. ATR-FTIR and EXAFS Study of the Aqueous Zn(II)/Oxalate/Hematite Ternary System
journal, March 2009
- Ha, Juyoung; Trainor, Thomas P.; Farges, François
- Langmuir, Vol. 25, Issue 10
The excretion of citric and malic acid by proteoid roots ofLupinus albus L.; effects on soil solution concentrations of phosphate, iron, and aluminum in the proteoid rhizosphere in samples of an oxisol and a luvisol
journal, January 1994
- Gerke, Jörg; Römer, Wilhelm; Jungk, Albrecht
- Zeitschrift für Pflanzenernährung und Bodenkunde, Vol. 157, Issue 4
Zinc Adsorption by a Lateritic Soil in the Presence of Organic Ligands
journal, September 1990
- Chairidchai, P.; Ritchie, G. S. P.
- Soil Science Society of America Journal, Vol. 54, Issue 5
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
SIXPack a Graphical User Interface for XAS Analysis Using IFEFFIT
journal, January 2005
- Webb, S. M.
- Physica Scripta
IFEFFIT : interactive XAFS analysis and FEFF fitting
journal, March 2001
- Newville, Matthew
- Journal of Synchrotron Radiation, Vol. 8, Issue 2
Synthesis and characterization of nickel and magnesium ferrites obtained from α-NaFeO2
journal, September 1993
- Blesa, M.; Amador, U.; Moran, E.
- Solid State Ionics, Vol. 63-65
Real-space multiple-scattering calculation and interpretation of x-ray-absorption near-edge structure
journal, September 1998
- Ankudinov, A. L.; Ravel, B.; Rehr, J. J.
- Physical Review B, Vol. 58, Issue 12
Interaction of Fe(II) with phosphate and sulfate on iron oxide surfaces
journal, June 2015
- Hinkle, Margaret A. G.; Wang, Zimeng; Giammar, Daniel E.
- Geochimica et Cosmochimica Acta, Vol. 158
Simulated atmospheric processing of iron oxyhydroxide minerals at low pH: Roles of particle size and acid anion in iron dissolution
journal, April 2010
- Rubasinghege, G.; Lentz, R. W.; Scherer, M. M.
- Proceedings of the National Academy of Sciences, Vol. 107, Issue 15
Trace element cycling through iron oxide minerals during redox-driven dynamic recrystallization
journal, November 2011
- Frierdich, Andrew J.; Luo, Yun; Catalano, Jeffrey G.
- Geology, Vol. 39, Issue 11
Adsorption of organic matter at mineral/water interfaces: I. ATR-FTIR spectroscopic and quantum chemical study of oxalate adsorbed at boehmite/water and corundum/water interfaces
journal, November 2004
- Yoon, Tae Hyun; Johnson, Stephen B.; Musgrave, Charles B.
- Geochimica et Cosmochimica Acta, Vol. 68, Issue 22
Adsorption of Organic Matter at Mineral/Water Interfaces: 3. Implications of Surface Dissolution for Adsorption of Oxalate
journal, December 2004
- Johnson, Stephen B.; Yoon, Tae Hyun; Slowey, Aaron J.
- Langmuir, Vol. 20, Issue 26
Formation of Ternary Metal-Oxalate Surface Complexes on α-FeOOH Particles
journal, October 2011
- Simanova, Anna A.; Loring, John S.; Persson, Per
- The Journal of Physical Chemistry C, Vol. 115, Issue 43
Adsorption of oxalate and malonate at the water-goethite interface: Molecular surface speciation from IR spectroscopy
journal, February 2005
- Persson, Per; Axe, Kristina
- Geochimica et Cosmochimica Acta, Vol. 69, Issue 3
Time-dependent surface speciation of oxalate at the water-boehmite (γ-AlOOH) interface: implications for dissolution
journal, December 2001
- Axe, Kristina; Persson, Per
- Geochimica et Cosmochimica Acta, Vol. 65, Issue 24
Works referencing / citing this record:
Influence of low molecular weight anionic ligands on the sorption of heavy metals by soil constituents: a review
journal, April 2019
- Zhu, Jun; Fu, Qingling; Qiu, Guohong
- Environmental Chemistry Letters, Vol. 17, Issue 3