Hostname: page-component-cd9895bd7-lnqnp Total loading time: 0 Render date: 2024-12-23T18:06:13.358Z Has data issue: false hasContentIssue false
  • English
  • Français

Fe isotope fractionation during the precipitation of ferrihydrite and transformation of ferrihydrite to goethite

Published online by Cambridge University Press:  05 July 2018

R. E. Clayton ,
K. A. Hudson-Edwards ,
D. Malinovsky  and
P. Andersson
R. E. Clayton
Affiliation:
Research School of Earth Sciences at UCL-Birkbeck, Gower St., London WC1E 6BT, UK
K. A. Hudson-Edwards*
Affiliation:
Research School of Earth Sciences at UCL-Birkbeck, Gower St., London WC1E 6BT, UK
D. Malinovsky
Affiliation:
Division of Applied Geology, Luleå University of Technology, S-971 87 Luleå, Sweden
P. Andersson
Affiliation:
Laboratory for Isotope Geology, Swedish Museum of Natural History, Box 50007, 104 05 Stockholm, Sweden
*
*E-mail: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

Ferrihydrite and goethite are amongst the most important substrates for the sorption of contaminants in soil and other environmental media. Isotopic studies of the transition elements, particularly those that exhibit more than one oxidation state and show pH- and/or redox-sensitive behaviour at low temperatures, have been shown to be potentially useful present-day and past proxies for redox (or palaeoredox) conditions. We have made preliminary investigations of Fe isotope fractionation that take place during the formation of FeIII (oxy)hydroxides (FeIIIox) from an aqueous FeIII(NO3)3 solution (FeIIIaq) under laboratory conditions. We have attempted to keep the chemical system simple by excluding 'vital effects' and major changes in redox through the maintenance of abiotic conditions and use of FeIIIaq. Isotopic measurements (56Fe/54Fe, 57Fe/54Fe) of the FeIII(NO3)3 stock solution, the original ferrihydrite and the mixed ferrihydrite/goethite-supernatant FeIIIaq 'pairs' were carried out using a double focusing multicollector inductively coupled plasma mass spectrometer. The results reveal an apparent systematic variation indicating larger ΔFeIIIaq—FeIIIox with decrease in the ferrihydrite:goethite ratio, which reflects the time allowed for isotopic exchange. These values range from virtually zero (0.03%) after 24 h to 0.30% after 70 h. In each FeIIIox-FeIIIaq 'pair' the lighter Fe isotope is partitioned into the FeIIIox, leaving the FeIIIaq isotopically heavier. The observed fractionation reflects isotopic exchange of Fe between the FeIIIox and FeIIIaq upon at least a two step transition of ferrihydrite to goethite.

Keywords

ferrihydritegoethitetransformationiron isotopefractionationferric nitrate
Type
Research Article
Information
Mineralogical Magazine , Volume 69 , Issue 5 , October 2005 , pp. 667 - 676
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2005

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Footnotes

†

Deceased

References

Anbar, A.D. (2004) Iron stable isotopes: beyond biosignatures. Earth and Planetary Science Letters, 217, 223–236.CrossRefGoogle Scholar
Anbar, A.D., Roe, J.E., Barling, J. and Nealson, K.H. (2000) Nonbiological fractionation of Fe isotopes. Science, 288, 126–128.CrossRefGoogle Scholar
Anbar, A.D., Knab, K. and Barling, J. (2001) Precise determination of mass-dependent variations in the isotopic composition of Mo using MC-ICP-MS. Analytical Chemistry, 73, 1425.CrossRefGoogle Scholar
Andrén, H., Rodushkin, I., Stenberg, A., Malinovsky, D. and Baxter, D.C. (2004) Sources of mass bias and isotope ratio variation in multi-collector ICP-MS: optimization of instrumental parameters based on experimental observations. Journal of Analytical Atomic Spectrometry, 19, 1217–1224.CrossRefGoogle Scholar
Beard, B.L. and Johnson, C.M. (2004) Fe isotope variations in the modern and ancient Earth and other planetary bodies. Pp. 319–357 in: Biomineralization (Dove, P.M., de Yoreo, J.J. and Weiner, S., editors). Reviews in Mineralogy and Geochemistry, 55, Mineralogical Society of America and the Geochemical Society, Washington, D.C.Google Scholar
Brantley, S.L., Liermann, L.J., Guynn, R.L., Anbar, A., Icopini, G.A. and Barling, J. (2004) Fe isotopic fractionation during mineral dissolution with and without bacteria. Geochimica et Cosmochimica Acta, 68, 3189–3204.CrossRefGoogle Scholar
Bullen, T.D. and McMahon, P.M. (1998) Using stable Fe isotopes to assess microbially-mediated Fe3+reduction in a jet-fuel contaminated aquifer. Mineralogical Magazine, 62A, 255—256.CrossRefGoogle Scholar
Bullen, T.D., White, A.F., Childs, C.W. Vivet, D.V. and Schultz, M.S. (2001) Demonstration of significant abiotic iron isotope fractionation in nature. Geology, 29, 699–702.2.0.CO;2>CrossRefGoogle Scholar
Bullen, T.D., White, A., Mandernack, K. and Witte, K. (2002) Iron isotope fractionation: does equilibrium or disequilibrium rule? Geochimica et Cosmochimica Acta, 66, A110.Google Scholar
Cardinal, D., Alleman, L.Y., de Jong, J., Ziegler, K. and Andre, L. (2003) Isotopic composition of silicon measured by multicollector plasma source mass spectrometry in dry plasma mod. Journal of Analytical Atomic Spectrometry, 18, 213—218.CrossRefGoogle Scholar
Criss, R.E. (1999) Principles of Stable Isotope Distribution. Oxford University Press, New York.CrossRefGoogle Scholar
Croal, L.R., Johnson, C.M., Beard, B.L. and Newman, D.K. (2004) Iron isotope fractionation by Fe(U)-oxidizing photoautotrophic bacteria. Geochimica et Cosmochimica Acta, 68, 1227–1242.CrossRefGoogle Scholar
Feitknecht, W. and Michaelis, W. (1962) Über die Hydrolyse von Fe3+-Perchloratlösungen. Helvetica Chimica Acta, 26, 212–214.CrossRefGoogle Scholar
Hair, NJ. and Beattie, J.K. (1977) Structure of hexaqua iron (III) nitrate trihydrate. Comparison of iron (II) and iron (III) bond lengths in high-spin octahedral environments. Inorganic Chemistry, 16, 245—250.CrossRefGoogle Scholar
Hudson-Edwards, K.A., Jamieson, H.E., Charnock, J.M. and Macklin, M.G. (2005) Arsenic speciation in waters and sediment of ephemeral floodplain pools, Rios Agrio-Guadiamar, Aznalcollar, Spain. Chemical Geology, 219, 175–192.CrossRefGoogle Scholar
Jenne, E.A. (1968) Controls on Mn, Fe, Co, Ni, Cu, and Zn concentrations in soils and water: the significant role of hydrous Mn and Fe oxides. Advances in Chemistry Series, 73, 337–388.CrossRefGoogle Scholar
Johnson, C.A. (1986) The regulation of trace element concentrations in river and estuarine waters contaminated with acid mine drainage: The adsorption of Cu and Zn on amorphous Fe oxyhydroxide. Geochimica et Cosmochimica Acta, 50, 2433—2438.CrossRefGoogle Scholar
Johnson, C.M., Beard, B.L. and Albarède, F., editors (2004) Geochemistry of Non-traditional Stable Isotopes. Reviews in Mineralogy and Geochemistry, 55, Mineralogical Society of America and the Geochemical Society, Washington, D.C.CrossRefGoogle Scholar
Johnson, C.M., Skulan, J.L., Beard, B.L., Sun, H., Nealson, K.H. and Braterman, P.S. (2002) Isotopic fractionation between Fe(ni) and Fe(U) in aqueous solutions. Earth and Planetary Science Letters, 195, 141–153.CrossRefGoogle Scholar
Kukkadapu, R.K., Zachara, J.M., Fredrickson, J.K., Smith, S.C, Dohnalkova, A.C and Russell, C.K. (2003) Transformation of 2-line ferrihydrite to 6-line ferrihydrite under oxic and anoxic conditions. American Mineralogist, 88, 1903–1914.CrossRefGoogle Scholar
Malinovsky, D., Stenberg, A., Rodushkin, I., Andren, H., Ingri, J., Öhlander, B. and Baxter, D.C. (2003) Performance of high resolution MC-ICP-MS for Fe isotope ratio measurements in sedimentary geologic materials. Journal of Analytical Atomic Spectrometry, 18, 687–695.CrossRefGoogle Scholar
Mandernack, K.W., Bullen, T.D., Shanks, W.S. and Emerson, D. (2002) Stable oxygen and iron isotopic analyses of biotic and abiotic iron oxides precipitated in stream waters and in laboratory synthesis experiments. International Association of Geochemistry and Cosmochemistry, 4thInternational Symposium on Applied Isotope Geochemistry (AIG-IV), Pacific Grove, California, USA, Program and Abstracts, 7.Google Scholar
Marechal, C., Télouk, P. and Albarède, F. (1999) Precise analysis of copper and zinc isotope compositions by plasma source mass spectrometry. Chemical Geology, 156, 251–273.CrossRefGoogle Scholar
Matthews, A., Zhu, X.-K. and O'Nions, R.K. (2001) Kinetic iron stable isotope fractionation between iron (-II) and (-III) complexes in solution. Earth and Planetary Science Letters, 192, 81–92.CrossRefGoogle Scholar
O'Neil, J.R. (1986) Theoretical and experimental aspects of isotopic fractionation. Pp. 1–40 in: Stable Isotopes in High Temperature Geological Processes (Valley, J.W.,H.P., Taylor Jr. and O'Neil, J.R., editors). Reviews in Mineralogy, 16, Mineralogical Society of America, Washington D.C.Google Scholar
Parkman, R.H., Charnock, J.M., Bryan, N.D., Livens, F.R. and Vaughan, D.J. (1999) Reactions of copper and cadmium ions in aqueous solution with goethite, lepidocrocite, mackinawite and pyrite. American Mineralogist, 84, 407–419.CrossRefGoogle Scholar
Roe, J.E., Anbar, A.D. and Barling, J. (2003) Nonbiological fractionation of Fe isotopes: evidence of an equilibrium isotope effect. Chemical Geology, 195, 69–85.CrossRefGoogle Scholar
Schauble, E.A. (2004) Applying stable isotope fractionation theory to new systems. Pp. 65–111 in: Geochemistry of Non-traditional Stable Isotopes (Johnson, CM., Beard, B.L. and Albarède, F., editors). Reviews in Mineralogy and Geochemistry, 55. Mineralogical Society of America and the Geochemical Society, Washington, D.C.CrossRefGoogle Scholar
Schwertmann, U. and Cornell, R.M. (1991) Iron Oxides in the Laboratory: Preparation and Characterization. VCH Publishers, Weinheim, Germany, 91 pp.Google Scholar
Schwertmann, U. and Murad, E. (1983) Effect of pH on the formation of goethite and hematite from ferrihydrite. Clays and Clay Minerals, 4, 277–284.CrossRefGoogle Scholar
Skulan, J.L., Beard, B.L. and Johnson, C.M. (2002) Kinetic and equilibrium Fe isotope fractionation between aqueous Fe(III) and hematite. Geochimica et Cosmochimica Acta, 66, 2995–3015.CrossRefGoogle Scholar
Welch, S.A., Beard, B.L., Johnson, C.M. and Braterman, P.S. (2003) Kinetic and equilibrium Fe isotope fractionation between aqueous Fe(III) and Fe(III). Geochimica et Cosmochimica Acta, 67, 4231—4250.CrossRefGoogle Scholar
Wiesli, R.A., Beard, B.L. and Johnson, C.M. (2003) Experimental determination of Fe isotope fractionation between aq. Fe(II), ‘green rust’ and siderite. Geochimica et Cosmochimica Acta, 67, A533.Google Scholar
Woodhead, J. (2002) A simple method for obtaining highly accurate Pb isotope data by MC-ICP-MS. Journal of Analytical Atomic Spectrometry, 17, 1381–1385.CrossRefGoogle Scholar
Zhu, X.-K., O'Nions, R.K., Guo, Y. and Reynolds, B.C. (2000) Secular variation of iron isotopes in north Atlantic Deep Water. Science, 287, 2000–2002.CrossRefGoogle ScholarPubMed
Zhu, X.-K., Guo, Y., Williams, R.J.P., O'Nions, R.K., Matthews, A., Belshaw, N.S., Canters, G.W., de Waal, E.C., Weser, U., Burgess, B.K. and Salvato, B. (2002) Mass fractionation processes of transition metal isotopes. Earth and Planetary Science Letters, 200, 47–62.CrossRefGoogle Scholar