Simultaneous Adsorption and Incorporation of Sr 2+ at the Barite (001)–Water Interface

Bracco, Jacquelyn N.; Lee, Sang Soo; Stubbs, Joanne E.; Eng, Peter J.; Jindra, Sarah; Warren, D. Morgan; Kommu, Anitha; Fenter, Paul; Kubicki, James D.; Stack, Andrew G.

doi:10.1021/acs.jpcc.8b08848

Title: Simultaneous Adsorption and Incorporation of Sr ²⁺ at the Barite (001)–Water Interface

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Abstract

Ionically bonded minerals are ubiquitous and play a determinative role in controlling the mobility of toxic metals in natural environments. However, little is known about the mechanism of ion uptake by these mineral surfaces. Here, the sorption of strontium ions (Sr2+) to the barite (001)–water interface was studied using a combination of synchrotron X-ray scattering and three types of computational simulations (density functional theory, classical molecular dynamics (CMD), and CMD-metadynamics). In situ resonant anomalous X-ray reflectivity (RAXR) revealed that Sr2+ adsorbed on the barite surface as inner-sphere surface complexes and was incorporated within the outermost barite atomic layers. Density functional theory combined with CMD simulations confirmed the thermodynamic stability of these species, demonstrating almost equal magnitudes in the free energy of sorption between these species. Metadynamics simulations showed a more detailed feature in the free energy landscape for metal adsorption where adsorbed Sr2+ are stabilized in as many as four distinct inner-sphere sites and additional outer-sphere sites that are more diffuse and less energetically favorable than the inner-sphere sites. All three techniques confirmed Sr2+ adsorbs inner-sphere and binds to oxygens in the top two surface sulfate groups. The energy barriers among the inner-sphere sites were significantly lower compared with thosemore »« less

Authors:

^[1];

^[2]; Eng, Peter J. ^[2]; Jindra, Sarah ^[3]; Warren, D. Morgan ^[4]; Kommu, Anitha ^[5];

^[1];

^[5];

^[6]

Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Chicago, IL (United States)
Wright State University, Dayton, OH (United States)
Golder Associates Inc., Lakewood, CO (United States)
University of Texas at El Paso, TX (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Publication Date:: Wed Dec 19 00:00:00 EST 2018

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

OSTI Identifier:: 1493716

Alternate Identifier(s):: OSTI ID: 1493975

Grant/Contract Number:: AC02-06CH11357; FG02-94ER14466; AC02-05CH11231; AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 123; Journal Issue: 2; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-ray reflectivity; adsorption; barite; cation exchange; density functional theory; interface; isotherm; molecular dynamics; sorption; strontium

Citation Formats


                    Bracco, Jacquelyn N., Lee, Sang Soo, Stubbs, Joanne E., Eng, Peter J., Jindra, Sarah, Warren, D. Morgan, Kommu, Anitha, Fenter, Paul, Kubicki, James D., and Stack, Andrew G. Simultaneous Adsorption and Incorporation of Sr 2+ at the Barite (001)–Water Interface.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcc.8b08848.

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                    Bracco, Jacquelyn N., Lee, Sang Soo, Stubbs, Joanne E., Eng, Peter J., Jindra, Sarah, Warren, D. Morgan, Kommu, Anitha, Fenter, Paul, Kubicki, James D., & Stack, Andrew G. Simultaneous Adsorption and Incorporation of Sr 2+ at the Barite (001)–Water Interface.  United States.  https://doi.org/10.1021/acs.jpcc.8b08848

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                    Bracco, Jacquelyn N., Lee, Sang Soo, Stubbs, Joanne E., Eng, Peter J., Jindra, Sarah, Warren, D. Morgan, Kommu, Anitha, Fenter, Paul, Kubicki, James D., and Stack, Andrew G. Wed .  
"Simultaneous Adsorption and Incorporation of Sr 2+ at the Barite (001)–Water Interface".  United States.  https://doi.org/10.1021/acs.jpcc.8b08848.  https://www.osti.gov/servlets/purl/1493716.

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@article{osti_1493716,

  title        = {Simultaneous Adsorption and Incorporation of Sr 2+ at the Barite (001)–Water Interface},

  author       = {Bracco, Jacquelyn N. and Lee, Sang Soo and Stubbs, Joanne E. and Eng, Peter J. and Jindra, Sarah and Warren, D. Morgan and Kommu, Anitha and Fenter, Paul and Kubicki, James D. and Stack, Andrew G.},

  abstractNote = {Ionically bonded minerals are ubiquitous and play a determinative role in controlling the mobility of toxic metals in natural environments. However, little is known about the mechanism of ion uptake by these mineral surfaces. Here, the sorption of strontium ions (Sr2+) to the barite (001)–water interface was studied using a combination of synchrotron X-ray scattering and three types of computational simulations (density functional theory, classical molecular dynamics (CMD), and CMD-metadynamics). In situ resonant anomalous X-ray reflectivity (RAXR) revealed that Sr2+ adsorbed on the barite surface as inner-sphere surface complexes and was incorporated within the outermost barite atomic layers. Density functional theory combined with CMD simulations confirmed the thermodynamic stability of these species, demonstrating almost equal magnitudes in the free energy of sorption between these species. Metadynamics simulations showed a more detailed feature in the free energy landscape for metal adsorption where adsorbed Sr2+ are stabilized in as many as four distinct inner-sphere sites and additional outer-sphere sites that are more diffuse and less energetically favorable than the inner-sphere sites. All three techniques confirmed Sr2+ adsorbs inner-sphere and binds to oxygens in the top two surface sulfate groups. The energy barriers among the inner-sphere sites were significantly lower compared with those for constituent cation Ba2+, implying fast exchange among adsorbed Sr2+ species. The Sr2+ uptake measured by RAXR followed a Frumkin isotherm defined with an apparent free energy of sorption, ΔGSr ≈ – 22 kJ/mol, and an effective attractive interaction constant, γ ≈ – 4.5 kJ/mol, between sorbed Sr2+. While the observed free energy can be mostly explained by the (CMD) Helmholtz free energy of adsorption for Sr2+, ΔFSr = -15.3 kJ/mol, the origin of the sorbate–sorbate correlation could not be fully described by our computational work. Together, these experimental and computational results demonstrate the complexity of Sr2+ sorption behavior at the barite (001) surface.},

  doi          = {10.1021/acs.jpcc.8b08848},

  journal      = {Journal of Physical Chemistry. C},

  number       = 2,

  volume       = 123,

  place        = {United States},

  year         = {Wed Dec 19 00:00:00 EST 2018},

  month        = {Wed Dec 19 00:00:00 EST 2018}

}

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Title: Simultaneous Adsorption and Incorporation of Sr 2+ at the Barite (001)–Water Interface

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Title: Simultaneous Adsorption and Incorporation of Sr ²⁺ at the Barite (001)–Water Interface