Quantification of Coexisting Inner- and Outer-Sphere Complexation of Sulfate on Hematite Surfaces

Wang, Xiaoming; Wang, Zimeng; Peak, Derek; Tang, Yadong; Feng, Xionghan; Zhu, Mengqiang

doi:10.1021/acsearthspacechem.7b00154

Quantification of Coexisting Inner- and Outer-Sphere Complexation of Sulfate on Hematite Surfaces

Journal Article · Thu Mar 01 23:00:00 EST 2018 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.7b00154· OSTI ID:1434729

Wang, Xiaoming ^[1]; Wang, Zimeng ^[2]; Peak, Derek ^[3]; Tang, Yadong ^[4]; ^[4]; ^[5]

Huazhong Agricultural Univ., (China); Univ. of Wyoming, Laramie, WY (United States)
Louisiana State Univ., Baton Rouge, LA (United States)
Univ. of Saskatchewan, Saskatoon, SK (Canada)
Huazhong Agricultural Univ., (China)
Univ. of Wyoming, Laramie, WY (United States)

Sulfate adsorption on hematite surfaces controls sulfate mobility and environmental behavior but whether sulfate forms both inner- and outer-sphere complexes and the type of the inner-sphere complexes remain contentious. With ionic strength tests and S K-edge X-ray absorption near-edge structure spectroscopy, we show that sulfate forms both outer- and inner-sphere complexes on hematite surfaces. Both S K-edge extended X-ray absorption fine structure spectroscopy and the differential pair distribution function analyses determine the S–Fe interatomic distance (~3.24 Å) of the inner-sphere complex, suggesting bidentate-binuclear complexation. A multivariate curve resolution (MCR) analysis of the attenuated total reflection–Fourier-transform infrared spectra of adsorption envelope samples shows that increasing ionic strength does not affect the inner-sphere but decreases the outer-sphere complex adsorption loading, consistent with the ionic strength effect. The extended triple layer model directly and successfully models the MCR-derived inner- and outer-sphere surface loadings at various ionic strengths, indicating weaker sulfate inner-sphere complexation on hematite than on ferrihydrite surfaces. Results also show that sample drying, lower pH, and higher ionic strength all favor sulfate inner-sphere complexation, but the hematite particle size does not affect the relative proportions of the two types of complexes. Sulfate adsorption kinetics show increasing ratio of exchanged OH– to adsorbed sulfate with time, attributed to inner- and outer-sphere complexation dominating at different adsorption stages and to the changes of the relative abundance of surface OH^– and H₂O groups with time. This work clarifies sulfate adsorption mechanisms on hematite and has implications for understanding sulfate availability, behavior and fate in the environment. Our work suggests that the simple macroscopic ionic strength test correlates well with directly measured outer-sphere complexes.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (US). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1434729

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 4 Vol. 2; ISSN 2472-3452

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

References (58)

The Iron Oxides Cornell, R. M.; Schwertmann, U. https://doi.org/10.1002/3527602097	book	July 2003
The Mechanism of Selenate Adsorption on Goethite and Hydrous Ferric Oxide Manceau, Alain; Charlet, Laurent Journal of Colloid and Interface Science, Vol. 168, Issue 1 https://doi.org/10.1006/jcis.1994.1396	journal	November 1994
In SituFourier Transform Infrared Measurements of Sulfate Adsorption on Hematite in Aqueous Solutions Hug, Stephan J. Journal of Colloid and Interface Science, Vol. 188, Issue 2 https://doi.org/10.1006/jcis.1996.4755	journal	April 1997
Mechanism of the Shape and Structure Control of Monodispersed α-Fe2O3Particles by Sulfate Ions Sugimoto, Tadao; Wang, Yinsheng Journal of Colloid and Interface Science, Vol. 207, Issue 1 https://doi.org/10.1006/jcis.1998.5741	journal	November 1998
An in Situ ATR-FTIR Investigation of Sulfate Bonding Mechanisms on Goethite Peak, Derek; Ford, Robert G.; Sparks, Donald L. Journal of Colloid and Interface Science, Vol. 218, Issue 1 https://doi.org/10.1006/jcis.1999.6405	journal	October 1999
Sulfate Adsorption on Goethite Rietra, René P. J. J.; Hiemstra, Tjisse; van Riemsdijk, Willem H. Journal of Colloid and Interface Science, Vol. 218, Issue 2 https://doi.org/10.1006/jcis.1999.6408	journal	October 1999
Vibrational Spectroscopy Study of Selenate and Sulfate Adsorption Mechanisms on Fe and Al (Hydr)oxide Surfaces Wijnja, Hotze; Schulthess, Cristian P. Journal of Colloid and Interface Science, Vol. 229, Issue 1 https://doi.org/10.1006/jcis.2000.6960	journal	September 2000
Comparison of Selenate and Sulfate Adsorption on Goethite Rietra, René P. J. J.; Hiemstra, Tjisse; van Riemsdijk, Willem H. Journal of Colloid and Interface Science, Vol. 240, Issue 2 https://doi.org/10.1006/jcis.2001.7650	journal	August 2001
Irreversibility of sulfate sorption on goethite and hematite Turner, Laurie J.; Kramer, James R. Water, Air, & Soil Pollution, Vol. 63, Issue 1-2 https://doi.org/10.1007/BF00475619	journal	May 1992
Surface ionization and complexation at the oxide/water interface. 3. Adsorption of anions Davis, James A.; Leckie, James O. Journal of Colloid and Interface Science, Vol. 74, Issue 1 https://doi.org/10.1016/0021-9797(80)90168-X	journal	March 1980
Standard states for the activities of mineral surface sites and species Sverjensky, Dimitri A. Geochimica et Cosmochimica Acta, Vol. 67, Issue 1 https://doi.org/10.1016/S0016-7037(02)01074-8	journal	January 2003
Evaluation of internally consistent parameters for the triple-layer model by the systematic analysis of oxide surface titration data Sahai, Nita; Sverjensky, Dimitri A. Geochimica et Cosmochimica Acta, Vol. 61, Issue 14 https://doi.org/10.1016/S0016-7037(97)00128-2	journal	July 1997
Surface Complexation of Sulfate by Hematite Surfaces: FTIR and STM Observations Eggleston, Carrick M.; Hug, Stephan; Stumm, Werner Geochimica et Cosmochimica Acta, Vol. 62, Issue 4 https://doi.org/10.1016/S0016-7037(97)00372-4	journal	February 1998
The relationship between molecular structure and ion adsorption on variable charge minerals Rietra, René P. J. J.; Hiemstra, Tjisse; van Riemsdijk, Willem H. Geochimica et Cosmochimica Acta, Vol. 63, Issue 19-20 https://doi.org/10.1016/S0016-7037(99)00228-8	journal	October 1999
P and S K-edge XANES of transition-metal phosphates and sulfates Okude, N.; Nagoshi, M.; Noro, H. Journal of Electron Spectroscopy and Related Phenomena, Vol. 101-103 https://doi.org/10.1016/S0368-2048(98)00341-7	journal	June 1999
Surface complexation modeling for sulfate adsorption on ferrihydrite consistent with in situ infrared spectroscopic observations Fukushi, Keisuke; Aoyama, Kazuki; Yang, Chen Applied Geochemistry, Vol. 36 https://doi.org/10.1016/j.apgeochem.2013.06.013	journal	September 2013
In situ Fourier-transform infrared spectroscopy studies of inorganic ions adsorption on metal oxides and hydroxides Lefèvre, G. Advances in Colloid and Interface Science, Vol. 107, Issue 2-3 https://doi.org/10.1016/j.cis.2003.11.002	journal	March 2004
A test of geochemical reactivity as a function of mineral size: Manganese oxidation promoted by hematite nanoparticles Madden, Andrew S.; Hochella, Michael F. Geochimica et Cosmochimica Acta, Vol. 69, Issue 2 https://doi.org/10.1016/j.gca.2004.06.035	journal	January 2005
Prediction of the speciation of alkaline earths adsorbed on mineral surfaces in salt solutions Sverjensky, Dimitri A. Geochimica et Cosmochimica Acta, Vol. 70, Issue 10 https://doi.org/10.1016/j.gca.2006.01.006	journal	May 2006
A surface complexation model for sulfate and selenate on iron oxides consistent with spectroscopic and theoretical molecular evidence Fukushi, Keisuke; Sverjensky, Dimitri A. Geochimica et Cosmochimica Acta, Vol. 71, Issue 1 https://doi.org/10.1016/j.gca.2006.08.048	journal	January 2007
Studies of Cd(II)–sulfate interactions at the goethite–water interface by ATR-FTIR spectroscopy Zhang, G. Y.; Peak, D. Geochimica et Cosmochimica Acta, Vol. 71, Issue 9 https://doi.org/10.1016/j.gca.2006.12.020	journal	May 2007
Goethite adsorption of Cu(II), Pb(II), Cd(II), and Zn(II) in the presence of sulfate: Properties of the ternary complex Swedlund, Peter J.; Webster, Jenny G.; Miskelly, Gordon M. Geochimica et Cosmochimica Acta, Vol. 73, Issue 6 https://doi.org/10.1016/j.gca.2008.12.007	journal	March 2009
A surface structural model for ferrihydrite I: Sites related to primary charge, molar mass, and mass density Hiemstra, Tjisse; Van Riemsdijk, Willem H. Geochimica et Cosmochimica Acta, Vol. 73, Issue 15 https://doi.org/10.1016/j.gca.2009.04.032	journal	August 2009
Interaction of Fe(II) with phosphate and sulfate on iron oxide surfaces Hinkle, Margaret A. G.; Wang, Zimeng; Giammar, Daniel E. Geochimica et Cosmochimica Acta, Vol. 158 https://doi.org/10.1016/j.gca.2015.02.030	journal	June 2015
Inner- and outer-sphere complexation of ions at the goethite–solution interface Rahnemaie, Rasoul; Hiemstra, Tjisse; van Riemsdijk, Willem H. Journal of Colloid and Interface Science, Vol. 297, Issue 2 https://doi.org/10.1016/j.jcis.2005.11.003	journal	May 2006
An ATR-FTIR study of sulphate sorption on magnetite; rate of adsorption, surface speciation, and effect of calcium ions Roonasi, Payman; Holmgren, Allan Journal of Colloid and Interface Science, Vol. 333, Issue 1 https://doi.org/10.1016/j.jcis.2008.12.080	journal	May 2009
Sulfate adsorption at the buried hematite/solution interface investigated using total internal reflection (TIR)-Raman spectroscopy Jubb, Aaron M.; Verreault, Dominique; Posner, Ralf Journal of Colloid and Interface Science, Vol. 400 https://doi.org/10.1016/j.jcis.2013.02.031	journal	June 2013
Sorption of sulfate ions onto hematite studied by attenuated total reflection-infrared spectroscopy: Kinetics and competition with other ions Lefèvre, G.; Fédoroff, M. Physics and Chemistry of the Earth, Parts A/B/C, Vol. 31, Issue 10-14 https://doi.org/10.1016/j.pce.2006.04.001	journal	January 2006
Sulfate Local Coordination Environment in Schwertmannite Wang, Xiaoming; Gu, Chunhao; Feng, Xionghan Environmental Science & Technology, Vol. 49, Issue 17 https://doi.org/10.1021/acs.est.5b02660	journal	August 2015
Mechanisms of Chromate, Selenate, and Sulfate Adsorption on Al-Substituted Ferrihydrite: Implications for Ferrihydrite Surface Structure and Reactivity Johnston, Chad P.; Chrysochoou, Maria Environmental Science & Technology, Vol. 50, Issue 7 https://doi.org/10.1021/acs.est.5b05529	journal	March 2016
X-ray Absorption Spectroscopic Quantification and Speciation Modeling of Sulfate Adsorption on Ferrihydrite Surfaces Gu, Chunhao; Wang, Zimeng; Kubicki, James D. Environmental Science & Technology, Vol. 50, Issue 15 https://doi.org/10.1021/acs.est.6b00753	journal	July 2016
MINFIT: A Spreadsheet-Based Tool for Parameter Estimation in an Equilibrium Speciation Software Program Xie, Xiongfei; Giammar, Daniel E.; Wang, Zimeng Environmental Science & Technology, Vol. 50, Issue 20 https://doi.org/10.1021/acs.est.6b03399	journal	October 2016
Correction to X-ray Absorption Spectroscopic Quantification and Speciation Modeling of Sulfate Adsorption on Ferrihydrite Surfaces Gu, Chunhao; Wang, Zimeng; Kubicki, James D. Environmental Science & Technology, Vol. 51, Issue 11 https://doi.org/10.1021/acs.est.7b02036	journal	May 2017
Kinetics of Cation and Oxyanion Adsorption and Desorption on Ferrihydrite: Roles of Ferrihydrite Binding Sites and a Unified Model Tian, Lei; Shi, Zhenqing; Lu, Yang Environmental Science & Technology, Vol. 51, Issue 18 https://doi.org/10.1021/acs.est.7b03249	journal	August 2017
Ascorbate-Promoted Surface Iron Cycle for Efficient Heterogeneous Fenton Alachlor Degradation with Hematite Nanocrystals Huang, Xiaopeng; Hou, Xiaojing; Jia, Falong ACS Applied Materials & Interfaces, Vol. 9, Issue 10 https://doi.org/10.1021/acsami.6b16600	journal	March 2017
Binding Geometries of Silicate Species on Ferrihydrite Surfaces Wang, Xiaoming; Kubicki, James D.; Boily, Jean-François ACS Earth and Space Chemistry, Vol. 2, Issue 2 https://doi.org/10.1021/acsearthspacechem.7b00109	journal	January 2018
Shape Evolution Synthesis of Monodisperse Spherical, Ellipsoidal, and Elongated Hematite (α-Fe₂O₃) Nanoparticles Using Ascorbic Acid Tan, Wen-Feng; Yu, Ya-Ting; Wang, Ming-Xia Crystal Growth & Design, Vol. 14, Issue 1 https://doi.org/10.1021/cg401334d	journal	December 2013
Reactions on Mineral Dust Usher, Courtney R.; Michel, Amy E.; Grassian, Vicki H. Chemical Reviews, Vol. 103, Issue 12 https://doi.org/10.1021/cr020657y	journal	December 2003
Mechanisms of Selenate Adsorption on Iron Oxides and Hydroxides Peak, D.; Sparks, D. L. Environmental Science & Technology, Vol. 36, Issue 7 https://doi.org/10.1021/es0156643	journal	April 2002
Sorption of Uranium(VI) onto Ferric Oxides in Sulfate-Rich Acid Waters Walter, Marcus; Arnold, Thuro; Reich, Tobias Environmental Science & Technology, Vol. 37, Issue 13 https://doi.org/10.1021/es025749j	journal	July 2003
Speciation of Iron and Sulfate in Acid Waters: Aqueous Clusters to Mineral Precipitates Majzlan, Juraj; Myneni, Satish C. B. Environmental Science & Technology, Vol. 39, Issue 1 https://doi.org/10.1021/es049664p	journal	January 2005
Quantum Chemical Calculations of Sulfate Adsorption at the Al- and Fe-(Hydr)oxide-H ₂ O InterfaceEstimation of Gibbs Free Energies Paul, Kristian W.; Kubicki, James D.; Sparks, Donald L. Environmental Science & Technology, Vol. 40, Issue 24 https://doi.org/10.1021/es061139y	journal	November 2006
Mass Action Expressions for Bidentate Adsorption in Surface Complexation Modeling: Theory and Practice Wang, Zimeng; Giammar, Daniel E. Environmental Science & Technology, Vol. 47, Issue 9 https://doi.org/10.1021/es305180e	journal	April 2013
Effect of Ferrihydrite Crystallite Size on Phosphate Adsorption Reactivity Wang, Xiaoming; Li, Wei; Harrington, Richard Environmental Science & Technology, Vol. 47, Issue 18 https://doi.org/10.1021/es401301z	journal	August 2013
In Situ ATR FTIR Studies of SO ₄ Adsorption on Goethite in the Presence of Copper Ions Beattie, D. A.; Chapelet, J. K.; Gräfe, M. Environmental Science & Technology, Vol. 42, Issue 24 https://doi.org/10.1021/es801767b	journal	December 2008
FTIR Spectral Components of Schwertmannite Boily, Jean-François; Gassman, Paul L.; Peretyazhko, Tetyana Environmental Science & Technology, Vol. 44, Issue 4 https://doi.org/10.1021/es902803u	journal	January 2010
Structure of Sulfate Adsorption Complexes on Ferrihydrite Zhu, Mengqiang; Northrup, Paul; Shi, Chenyang Environmental Science & Technology Letters, Vol. 1, Issue 1 https://doi.org/10.1021/ez400052r	journal	October 2013
Charge trapping in the reductive dissolution of colloidal suspensions of iron(III) oxides Mulvaney, Paul; Cooper, Ronald; Grieser, Franz Langmuir, Vol. 4, Issue 5 https://doi.org/10.1021/la00083a028	journal	September 1988
Effect of Dehydration on Sulfate Coordination and Speciation at the Fe−(Hydr)oxide−Water Interface: A Molecular Orbital/Density Functional Theory and Fourier Transform Infrared Spectroscopic Investigation Paul, Kristian W.; Borda, Michael J.; Kubicki, James D. Langmuir, Vol. 21, Issue 24 https://doi.org/10.1021/la050648v	journal	October 2005
Effects of crystallite size on the structure and magnetism of ferrihydrite Wang, Xiaoming; Zhu, Mengqiang; Koopal, Luuk K. Environmental Science: Nano, Vol. 3, Issue 1 https://doi.org/10.1039/C5EN00191A	journal	January 2016
Phosphate and phytate adsorption and precipitation on ferrihydrite surfaces Wang, Xiaoming; Hu, Yongfeng; Tang, Yadong Environmental Science: Nano, Vol. 4, Issue 11 https://doi.org/10.1039/C7EN00705A	journal	January 2017
Simulated atmospheric processing of iron oxyhydroxide minerals at low pH: Roles of particle size and acid anion in iron dissolution Rubasinghege, G.; Lentz, R. W.; Scherer, M. M. Proceedings of the National Academy of Sciences, Vol. 107, Issue 15 https://doi.org/10.1073/pnas.0910809107	journal	April 2010
Sulfate ion Binding on Goethite and Hematite Turner, L. J.; Kramer, J. R. Soil Science, Vol. 152, Issue 3 https://doi.org/10.1097/00010694-199109000-00010	journal	September 1991
In Situ X-ray Absorption Study of Surface Complexes: Selenium Oxyanions on agr-FeOOH Hayes, K. F.; Roe, A. L.; Brown, G. E. Science, Vol. 238, Issue 4828 https://doi.org/10.1126/science.238.4828.783	journal	November 1987
Application of Kinetic Models to the Sorption of Copper(II) on to Peat Ho, Y. S.; McKay, G. Adsorption Science & Technology, Vol. 20, Issue 8 https://doi.org/10.1260/026361702321104282	journal	October 2002
The Mechanism of Sulfate Adsorption on Iron Oxides Parfitt, Roger L.; Smart, Roger St. C. Soil Science Society of America Journal, Vol. 42, Issue 1 https://doi.org/10.2136/sssaj1978.03615995004200010011x	journal	January 1978
Selenate and Selenite Sorption on Iron Oxides An Infrared and Electrophoretic Study Su, Chunming; Suarez, Donald L. Soil Science Society of America Journal, Vol. 64, Issue 1 https://doi.org/10.2136/sssaj2000.641101x	journal	January 2000
Adsorption-Desorption Processes in Subsurface Reactive Transport Modeling Goldberg, Sabine; Criscenti, Louise J.; Turner, David R. Vadose Zone Journal, Vol. 6, Issue 3 https://doi.org/10.2136/vzj2006.0085	journal	August 2007

Cited By (1)

Carbonate Adsorption to Ferrihydrite: Competitive Interaction with Phosphate for Use in Soil Systems Mendez, Juan C.; Hiemstra, Tjisse ACS Earth and Space Chemistry, Vol. 3, Issue 1 https://doi.org/10.1021/acsearthspacechem.8b00160	journal	December 2018

Figures / Tables (11)

Similar Records

An in situ ATR-FTIR investigation of sulfate bonding mechanisms on goethite

Journal Article · Fri Oct 01 00:00:00 EDT 1999 · Journal of Colloid and Interface Science · OSTI ID:20000028

Molecular-Scale Understanding of Sulfate Exchange from Schwertmannite by Chromate Versus Arsenate

Journal Article · Wed Apr 07 00:00:00 EDT 2021 · Environmental Science and Technology · OSTI ID:1819669

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ATR-FTIR spectroscopy
MCR analysis
S K-edge X-ray absorption spectroscopy
differential pair distribution function analysis
hematite
inner- and outer-sphere complexation
sulfate
surface complexation modeling

Quantification of Coexisting Inner- and Outer-Sphere Complexation of Sulfate on Hematite Surfaces

Citation Formats

References (58)

Cited By (1)

Figures / Tables (11)

Similar Records

Related Subjects