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Iron oxide mineralogy and stable iron isotope composition in a Gleysol with petrogleyic properties

  • SPECTRO-MICROSCOPIC CHARACTERIZATION OF BIOGEOCHEMICAL INTERFACES IN SOIL
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Abstract

Purpose

Properties of Fe oxides are poorly understood in soils with fluctuating water tables and variable redox conditions. The objective of this research was to (a) characterize the mineralogical composition of Fe oxides and (b) determine the relationship to the stable Fe isotope ratio in a soil with temporally and spatially sharp redox gradients.

Materials and methods

The lowland Gleysol (Petrogleyic) is in Northwest Germany and consists of oximorphic soil horizons (Ah 0–15, Bg 15–35, and CrBg 35–70 cm) developed from Holocene fluvial loam overlaying glaciofluvial sand with reductomorphic properties (2Cr horizon, +70 cm). Field measurements during the course of 28 months included the monitoring of groundwater table, soil redox potential, and analysis of the soil solutions. Solid Fe phases were studied by room temperature and cryogenic 57Fe Mössbauer spectroscopy, and stable Fe isotope compositions by multiple collector inductively coupled plasma mass spectrometry.

Results and discussion

The groundwater table ranged from −83 cm below to +8 cm above soil surface (median −27 cm). Permanent reducing conditions occurred in the 2Cr horizon with dissolved Fe concentrations of 44.8 mg L−1 (median). The duration of oxidizing conditions increased in the order CrBg < Bg < Ah. Total Fe increased from 50 (Ah) over 316 (Bg) up to 412 g kg−1 (CrBg) and was lowest in the 2Cr horizon (7 g kg−1). Ferrihydrite (51% of total Fe) was dominant over goethite (24%) in the Ah horizon. Conversely, nanogoethite dominated both the Bg (94%) and CrBg (86%) horizons. Iron in siderite amounted to 7% in the CrBg horizon. Iron isotope compositions yielded a range of δ 57Fe values from +0.29‰ (Ah horizon) to −0.30‰ (Bg horizon). In contrast to the overlying CrBg (δ 57Fe = −0.19‰) and Bg horizons, the 2Cr horizon is characterized by a relatively high δ 57Fe value of +0.22‰.

Conclusions

Lasting water saturation and frequent reducing conditions lead to the enrichment of goethite in subsoil. Once formed, goethite remains stable compared to ferrihydrite because it is less available for microbial mediated reductive dissolution. High δ 57Fe values in the topsoil primary result from fast ferrihydrite precipitation during aeration immediately after reducing conditions. In contrast, the low δ 57Fe values of the Fe-rich horizons (Bg, CrBg) promote adsorption of dissolved Fe with a light isotope composition onto goethite during capillary rise. The high δ 57Fe value of the Fe-poor subsoil (2Cr) is related to silicate-bound Fe rather than dissolution and precipitation of Fe oxides.

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Acknowledgments

For the assistance in the field and laboratory, we are grateful to Karin Greef, Julia Hurraß, Katrin Matern, Kristof Dorau, and Nadine Gorican. Ambre Luguet, University of Bonn, kindly helped to keep the Neptune operational. Jan Wiederhold from ETH Zürich is thanked for the Fe salt in-house isotope standard, Carsten Münker from the University of Köln for the BIR-1 reference material, and Hendrik Kathrein from Lanxess, Germany, for the Bayferrox 920Z goethite. This study was funded by the DFG (German Research Foundation) under the contract number Ma 2143/8-1 granted to T. Mansfeldt.

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Authors and Affiliations

  1. Department of Geosciences, Soil Geography/Soil Science, University of Cologne, Albertus-Magnus-Platz, 50923, Köln, Germany

    Tim Mansfeldt, Stephan Schuth & Mark Overesch

  2. Institute of Mineralogy, Leibniz University Hannover, Callinstraße 3, 30167, Hannover, Germany

    Stephan Schuth

  3. Soil Science, Technical University of Munich, Am Hochanger 2, 85354, Freising, Germany

    Werner Häusler

  4. Physics Department E15, Technical University of Munich, 85747, Garching, Germany

    Friedrich E. Wagner

  5. Federal Institute for Geosciences and Natural Resources (BGR), Stilleweg 2, 30655, Hannover, Germany

    Stephan Kaufhold

  6. M&O, Büro für Geowissenschaften, Südstraße 26b, 49751, Sögel, Germany

    Mark Overesch

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Mansfeldt, T., Schuth, S., Häusler, W. et al. Iron oxide mineralogy and stable iron isotope composition in a Gleysol with petrogleyic properties. J Soils Sediments 12, 97–114 (2012). https://doi.org/10.1007/s11368-011-0402-z

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