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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]
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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

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Footnotes

†

Deceased

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