Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

Frierdich, Andrew J.; Beard, Brian L.; Rosso, Kevin M.; Scherer, Michelle M.; Spicuzza, Michael J.; Valley, John W.; Johnson, Clark M.

doi:10.1016/j.gca.2015.03.029

Title: Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

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Abstract

The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Fe isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II)_aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II)_aq and goethite catalyzes O isotope exchange between the mineralmore »« less

Authors:

Frierdich, Andrew J. ^[1]; Beard, Brian L. ^[2]; Rosso, Kevin M. ^[3]; Scherer, Michelle M. ^[4]; Spicuzza, Michael J. ^[2]; Valley, John W. ^[2]; Johnson, Clark M. ^[2]

Univ. of Wisconsin, Madison, WI (United States); Univ. of Iowa, Iowa City, IA (United States)
Univ. of Wisconsin, Madison, WI (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of Iowa, Iowa City, IA (United States)

Publication Date:: Wed Jul 01 00:00:00 EDT 2015

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

Sponsoring Org.:: USDOE

OSTI Identifier:: 1203865

Report Number(s):: PNNL-SA-105541
Journal ID: ISSN 0016-7037; 47824; KC0302060

DOE Contract Number:: AC05-76RL01830

Resource Type:: Journal Article

Journal Name:: Geochimica et Cosmochimica Acta

Additional Journal Information:: Journal Volume: 160; Journal Issue: C; Journal ID: ISSN 0016-7037

Publisher:: The Geochemical Society; The Meteoritical Society

Country of Publication:: United States

Language:: English

Subject:: Environmental Molecular Sciences Laboratory

Citation Formats


                    Frierdich, Andrew J., Beard, Brian L., Rosso, Kevin M., Scherer, Michelle M., Spicuzza, Michael J., Valley, John W., and Johnson, Clark M. Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions.  United States: N. p., 2015. 
        Web.  doi:10.1016/j.gca.2015.03.029.

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                    Frierdich, Andrew J., Beard, Brian L., Rosso, Kevin M., Scherer, Michelle M., Spicuzza, Michael J., Valley, John W., & Johnson, Clark M. Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions.  United States.  https://doi.org/10.1016/j.gca.2015.03.029

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                    Frierdich, Andrew J., Beard, Brian L., Rosso, Kevin M., Scherer, Michelle M., Spicuzza, Michael J., Valley, John W., and Johnson, Clark M. 2015.  
        "Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions".  United States.  https://doi.org/10.1016/j.gca.2015.03.029.

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@article{osti_1203865,

  title        = {Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions},

  author       = {Frierdich, Andrew J. and Beard, Brian L. and Rosso, Kevin M. and Scherer, Michelle M. and Spicuzza, Michael J. and Valley, John W. and Johnson, Clark M.},

  abstractNote = {The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Fe isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II)aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II)aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II)aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous solutions, but presents a challenge for utilizing such an approach to determine equilibrium isotope fractionation factors. Despite the uncertainty from extrapolation, there is consistency in goethite-water fractionation factors for our reversal approach to equilibrium, with final weighted average fractionation factor values of Δ¹⁸OGth-wate r = 0.2 (±0.9‰) and 3.0 (±2.5‰) at 22 °C and -1.6 (±0.8‰) and 1.9 (±1.5‰) at 50 °C for micron-sized and nano-particulate goethite, respectively (errors at 2σ level). Reaction of ferrihydrite with Fe(II)aq in two distinct waters resulted in a quantitative conversion to goethite and complete O isotope exchange in each case, and similar fractionation factors were observed for experiments using the two waters. Comparison of our results with previous studies of O isotope fractionation between goethite and water suggests that particle size may be a contributing factor to the disparity among experimental studies.},

  doi          = {10.1016/j.gca.2015.03.029},

  url          = {https://www.osti.gov/biblio/1203865},
  journal      = {Geochimica et Cosmochimica Acta},

  issn         = {0016-7037},

  number       = C,

  volume       = 160,

  place        = {United States},

  year         = {Wed Jul 01 00:00:00 EDT 2015},

  month        = {Wed Jul 01 00:00:00 EDT 2015}

}

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