Formation and transformation of a short range ordered iron carbonate precursor

Knud Dideriksen, Cathrine Frandsen, Nicolas Bovet, Adam F. Wallace, Ozlem Sel, Tyler Arbour, Alexandra Navrotsky, James J. De Yoreo, Jillian F. Banfield

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

Fe(II)-carbonates, such as siderite, form in environments where O2 is scarce, e.g., during marine sediment diagenesis, corrosion and possibly CO2 sequestration, but little is known about their formation pathways. We show that early precipitates from carbonate solutions containing 0.1M Fe(II) with varying pH produced broad peaks in X-ray diffraction and contained dominantly Fe and CO3 when probed with X-ray photoelectron spectroscopy. Reduced pair distribution function (PDF) analysis shows only peaks corresponding to interatomic distances below 15Å, reflecting a material with no long range structural order. Moreover, PDF peak positions differ from those for known iron carbonates and hydroxides. Mössbauer spectra also deviate from those expected for known iron carbonates and suggest a less crystalline structure. These data show that a previously unidentified iron carbonate precursor phase formed. Its coherent scattering domains determined from PDF analysis are slightly larger than for amorphous calcium carbonate, suggesting that the precursor could be nanocrystalline. Replica exchange molecular dynamics simulations of Fe-carbonate polynuclear complexes yield PDF peak positions that agree well with those from experiments, offering the possibility that the material is a condensate of such complexes, assembled in a relatively unorganised fashion. If this is the case, the material could be nearly amorphous, rather than being composed of well defined nanocrystals. PDF measurements of samples ageing in solution coupled with refinement with the software PDFgui show that the material transforms to siderite or siderite/chukanovite mixtures within hours and that the transformation rate depends on pH. The identified Fe-carbonate precursor may potentially form during anaerobic corrosion or bacterial Fe reduction.
Original languageEnglish
JournalGeochimica Et Cosmochimica Acta
Volume164
Pages (from-to)94-109
Number of pages16
ISSN0016-7037
DOIs
Publication statusPublished - 2015

Cite this

Dideriksen, Knud ; Frandsen, Cathrine ; Bovet, Nicolas ; Wallace, Adam F. ; Sel, Ozlem ; Arbour, Tyler ; Navrotsky, Alexandra ; De Yoreo, James J. ; Banfield, Jillian F. / Formation and transformation of a short range ordered iron carbonate precursor. In: Geochimica Et Cosmochimica Acta. 2015 ; Vol. 164. pp. 94-109.
@article{ed2eb935f663424c9fc5c0998e0b4db3,
title = "Formation and transformation of a short range ordered iron carbonate precursor",
abstract = "Fe(II)-carbonates, such as siderite, form in environments where O2 is scarce, e.g., during marine sediment diagenesis, corrosion and possibly CO2 sequestration, but little is known about their formation pathways. We show that early precipitates from carbonate solutions containing 0.1M Fe(II) with varying pH produced broad peaks in X-ray diffraction and contained dominantly Fe and CO3 when probed with X-ray photoelectron spectroscopy. Reduced pair distribution function (PDF) analysis shows only peaks corresponding to interatomic distances below 15{\AA}, reflecting a material with no long range structural order. Moreover, PDF peak positions differ from those for known iron carbonates and hydroxides. M{\"o}ssbauer spectra also deviate from those expected for known iron carbonates and suggest a less crystalline structure. These data show that a previously unidentified iron carbonate precursor phase formed. Its coherent scattering domains determined from PDF analysis are slightly larger than for amorphous calcium carbonate, suggesting that the precursor could be nanocrystalline. Replica exchange molecular dynamics simulations of Fe-carbonate polynuclear complexes yield PDF peak positions that agree well with those from experiments, offering the possibility that the material is a condensate of such complexes, assembled in a relatively unorganised fashion. If this is the case, the material could be nearly amorphous, rather than being composed of well defined nanocrystals. PDF measurements of samples ageing in solution coupled with refinement with the software PDFgui show that the material transforms to siderite or siderite/chukanovite mixtures within hours and that the transformation rate depends on pH. The identified Fe-carbonate precursor may potentially form during anaerobic corrosion or bacterial Fe reduction.",
author = "Knud Dideriksen and Cathrine Frandsen and Nicolas Bovet and Wallace, {Adam F.} and Ozlem Sel and Tyler Arbour and Alexandra Navrotsky and {De Yoreo}, {James J.} and Banfield, {Jillian F.}",
year = "2015",
doi = "10.1016/j.gca.2015.05.005",
language = "English",
volume = "164",
pages = "94--109",
journal = "Geochimica et Cosmochimica Acta",
issn = "0016-7037",
publisher = "Pergamon Press",

}

Dideriksen, K, Frandsen, C, Bovet, N, Wallace, AF, Sel, O, Arbour, T, Navrotsky, A, De Yoreo, JJ & Banfield, JF 2015, 'Formation and transformation of a short range ordered iron carbonate precursor', Geochimica Et Cosmochimica Acta, vol. 164, pp. 94-109. https://doi.org/10.1016/j.gca.2015.05.005

Formation and transformation of a short range ordered iron carbonate precursor. / Dideriksen, Knud; Frandsen, Cathrine; Bovet, Nicolas; Wallace, Adam F.; Sel, Ozlem; Arbour, Tyler; Navrotsky, Alexandra; De Yoreo, James J.; Banfield, Jillian F.

In: Geochimica Et Cosmochimica Acta, Vol. 164, 2015, p. 94-109.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Formation and transformation of a short range ordered iron carbonate precursor

AU - Dideriksen, Knud

AU - Frandsen, Cathrine

AU - Bovet, Nicolas

AU - Wallace, Adam F.

AU - Sel, Ozlem

AU - Arbour, Tyler

AU - Navrotsky, Alexandra

AU - De Yoreo, James J.

AU - Banfield, Jillian F.

PY - 2015

Y1 - 2015

N2 - Fe(II)-carbonates, such as siderite, form in environments where O2 is scarce, e.g., during marine sediment diagenesis, corrosion and possibly CO2 sequestration, but little is known about their formation pathways. We show that early precipitates from carbonate solutions containing 0.1M Fe(II) with varying pH produced broad peaks in X-ray diffraction and contained dominantly Fe and CO3 when probed with X-ray photoelectron spectroscopy. Reduced pair distribution function (PDF) analysis shows only peaks corresponding to interatomic distances below 15Å, reflecting a material with no long range structural order. Moreover, PDF peak positions differ from those for known iron carbonates and hydroxides. Mössbauer spectra also deviate from those expected for known iron carbonates and suggest a less crystalline structure. These data show that a previously unidentified iron carbonate precursor phase formed. Its coherent scattering domains determined from PDF analysis are slightly larger than for amorphous calcium carbonate, suggesting that the precursor could be nanocrystalline. Replica exchange molecular dynamics simulations of Fe-carbonate polynuclear complexes yield PDF peak positions that agree well with those from experiments, offering the possibility that the material is a condensate of such complexes, assembled in a relatively unorganised fashion. If this is the case, the material could be nearly amorphous, rather than being composed of well defined nanocrystals. PDF measurements of samples ageing in solution coupled with refinement with the software PDFgui show that the material transforms to siderite or siderite/chukanovite mixtures within hours and that the transformation rate depends on pH. The identified Fe-carbonate precursor may potentially form during anaerobic corrosion or bacterial Fe reduction.

AB - Fe(II)-carbonates, such as siderite, form in environments where O2 is scarce, e.g., during marine sediment diagenesis, corrosion and possibly CO2 sequestration, but little is known about their formation pathways. We show that early precipitates from carbonate solutions containing 0.1M Fe(II) with varying pH produced broad peaks in X-ray diffraction and contained dominantly Fe and CO3 when probed with X-ray photoelectron spectroscopy. Reduced pair distribution function (PDF) analysis shows only peaks corresponding to interatomic distances below 15Å, reflecting a material with no long range structural order. Moreover, PDF peak positions differ from those for known iron carbonates and hydroxides. Mössbauer spectra also deviate from those expected for known iron carbonates and suggest a less crystalline structure. These data show that a previously unidentified iron carbonate precursor phase formed. Its coherent scattering domains determined from PDF analysis are slightly larger than for amorphous calcium carbonate, suggesting that the precursor could be nanocrystalline. Replica exchange molecular dynamics simulations of Fe-carbonate polynuclear complexes yield PDF peak positions that agree well with those from experiments, offering the possibility that the material is a condensate of such complexes, assembled in a relatively unorganised fashion. If this is the case, the material could be nearly amorphous, rather than being composed of well defined nanocrystals. PDF measurements of samples ageing in solution coupled with refinement with the software PDFgui show that the material transforms to siderite or siderite/chukanovite mixtures within hours and that the transformation rate depends on pH. The identified Fe-carbonate precursor may potentially form during anaerobic corrosion or bacterial Fe reduction.

U2 - 10.1016/j.gca.2015.05.005

DO - 10.1016/j.gca.2015.05.005

M3 - Journal article

VL - 164

SP - 94

EP - 109

JO - Geochimica et Cosmochimica Acta

JF - Geochimica et Cosmochimica Acta

SN - 0016-7037

ER -