Magnesium inhibition of calcite dissolution kinetics

Arvidson, Rolf S; Collier, Martin; Davis, Kevin J; Vinson, Michael D; Amonette, James E; Luttge, Andreas

doi:10.1016/j.gca.2005.10.005

Title: Magnesium inhibition of calcite dissolution kinetics

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Abstract

We present evidence of inhibition of calcite dissolution by dissolved magnesium through direct observations of the (104) surface using atomic force microscopy (AFM) and vertical scanning interferometry (VSI). Far from equilibrium, the pattern of magnesium inhibition is dependent on solution composition and specific to surface step geometry. In CO2-free solutions (pH 8.8), dissolved magnesium brings about little inhibition even at concentrations of 0.8 x 10-3 molal. At the same pH, magnesium concentrations of less than 0.05 x 10-3 molal in carbonate-buffered solutions generate significant inhibition, although no changes in surface and etch pit morphology are observed. As concentrations exceed magnesite saturation, the dissolution rate shows little additional decrease; however, selective pinning of step edges results in unique etch-pit profiles, seen in both AFM and VSI datasets. Despite the decreases in step velocity, magnesium addition in carbonated solutions also appears to activate the surface by increasing the nucleation rate of new defects. These relationships suggest that the modest depression of the bulk rate measured by VSI reflects a balance between competing reaction mechanisms that simultaneously depress the rate through selective inhibition of step movement, but also enhance reactivity on terraces by lowering the energy barrier to new etch-pit formation.

Authors:: Arvidson, Rolf S; Collier, Martin; Davis, Kevin J; Vinson, Michael D; Amonette, James E; Luttge, Andreas

Publication Date:: Wed Feb 01 00:00:00 EST 2006

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

Sponsoring Org.:: USDOE

OSTI Identifier:: 878670

Report Number(s):: PNNL-SA-49046
Journal ID: ISSN 0016-7037; GCACAK; 4391; KC0303020; TRN: US200611%%429

DOE Contract Number:: AC05-76RL01830

Resource Type:: Journal Article

Journal Name:: Geochimica et Cosmochimica Acta

Additional Journal Information:: Journal Volume: 70; Journal Issue: 3; Journal ID: ISSN 0016-7037

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; ATOMIC FORCE MICROSCOPY; CALCITE; DEFECTS; DISSOLUTION; GEOMETRY; INTERFEROMETRY; KINETICS; MAGNESIUM; MAGNESIUM ADDITIONS; MORPHOLOGY; NUCLEATION; REACTION KINETICS; SATURATION; VELOCITY; calcite; dissolution; magnesium; atomic force microscopy; AFM; vertical scanning interferometry; VSI; kinetics; carbonate; CO2; etch pit; surface chemistry; Environmental Molecular Sciences Laboratory

Citation Formats


                    Arvidson, Rolf S, Collier, Martin, Davis, Kevin J, Vinson, Michael D, Amonette, James E, and Luttge, Andreas. Magnesium inhibition of calcite dissolution kinetics.  United States: N. p., 2006. 
        Web.  doi:10.1016/j.gca.2005.10.005.

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                    Arvidson, Rolf S, Collier, Martin, Davis, Kevin J, Vinson, Michael D, Amonette, James E, & Luttge, Andreas. Magnesium inhibition of calcite dissolution kinetics.  United States.  https://doi.org/10.1016/j.gca.2005.10.005

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                    Arvidson, Rolf S, Collier, Martin, Davis, Kevin J, Vinson, Michael D, Amonette, James E, and Luttge, Andreas. 2006.  
        "Magnesium inhibition of calcite dissolution kinetics".  United States.  https://doi.org/10.1016/j.gca.2005.10.005.

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@article{osti_878670,

  title        = {Magnesium inhibition of calcite dissolution kinetics},

  author       = {Arvidson, Rolf S and Collier, Martin and Davis, Kevin J and Vinson, Michael D and Amonette, James E and Luttge, Andreas},

  abstractNote = {We present evidence of inhibition of calcite dissolution by dissolved magnesium through direct observations of the (104) surface using atomic force microscopy (AFM) and vertical scanning interferometry (VSI). Far from equilibrium, the pattern of magnesium inhibition is dependent on solution composition and specific to surface step geometry. In CO2-free solutions (pH 8.8), dissolved magnesium brings about little inhibition even at concentrations of 0.8 x 10-3 molal. At the same pH, magnesium concentrations of less than 0.05 x 10-3 molal in carbonate-buffered solutions generate significant inhibition, although no changes in surface and etch pit morphology are observed. As concentrations exceed magnesite saturation, the dissolution rate shows little additional decrease; however, selective pinning of step edges results in unique etch-pit profiles, seen in both AFM and VSI datasets. Despite the decreases in step velocity, magnesium addition in carbonated solutions also appears to activate the surface by increasing the nucleation rate of new defects. These relationships suggest that the modest depression of the bulk rate measured by VSI reflects a balance between competing reaction mechanisms that simultaneously depress the rate through selective inhibition of step movement, but also enhance reactivity on terraces by lowering the energy barrier to new etch-pit formation.},

  doi          = {10.1016/j.gca.2005.10.005},

  url          = {https://www.osti.gov/biblio/878670},
  journal      = {Geochimica et Cosmochimica Acta},

  issn         = {0016-7037},

  number       = 3,

  volume       = 70,

  place        = {United States},

  year         = {Wed Feb 01 00:00:00 EST 2006},

  month        = {Wed Feb 01 00:00:00 EST 2006}

}

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