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Manganese and iron oxide-coated redox bars as a tool to in situ study the element sorption in wet soils

  • Soils, Sec 4 • Ecotoxicology • Research Article
  • Published:
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Abstract

Purpose

When studying redox conditions in soils with manganese (Mn) and iron (Fe) oxide-coated redox bars, we observed the formation of Fe oxides along the Mn oxide coating and assumed sorption of other elements from soil solution to oxide surface. The objective of this study was to investigate the formation of Fe oxides along Mn redox bars and to analyze element sorption from soil solution to either Mn or Fe oxide along redox bar coatings.

Materials and methods

We protruded Mn redox bars into solutions with defined Fe2+ concentrations and removed the bars at distinct time intervals. The Mn oxide coating and potential Fe oxides were extracted using dithionite-citrate-bicarbonate (DCB). To investigate in situ element sorption behavior, we used previously field-installed redox bars, protruding these Mn redox bars into acidified hydroxylamine hydrochloride (AAH) to selectively extract Mn oxide and afterwards into DCB to dissolve the remaining Fe oxide coating. This two-step extraction procedure enabled the differentiation of elements bonded to either Mn or Fe oxide. Additionally, we analyzed the redox bar coatings at a very small scale (<1 mm2) via energy-dispersive x-ray spectroscopy (EDX).

Results and discussion

Iron oxides precipitated along the Mn oxide coating at low concentrations of 0.05 mg Fe2+ L−1, but did not trigger a color change. Although a change in color did occur instantaneously at 500 mg Fe2+ L−1, it is expected that Fe2+ concentrations are significantly lower under field conditions because ferrous Fe auto-oxidized within the artificial setup. Whereas Mn oxide sorbed cationic elements from the soil solution in the order Cu > Pb > Zn, Fe oxide preferentially sorbed oxyanions with As > P > Mo > V, respectively. “Field”-Fe oxides precipitating along the Mn redox bars sorbed elevated levels of As and P compared with the action of synthesized “lab”-Fe oxides along Fe redox bars, a finding which we attribute to short-range-ordered Fe phases with elevated sorption capacity.

Conclusions

Besides providing information regarding the monitoring of soil redox status, the developed sequential two-step extraction procedure enables the differentiation of the selective sorption of elements in the soil solution to the coating of Mn and Fe redox bars. The collection of Fe oxides formed naturally along the Mn redox bar coatings further enables the investigation of temporally and spatially diverse Fe oxide-forming processes.

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Acknowledgments

This study was financially supported by Verein der Freunde und Förderer der Universität zu Köln. We would like to thank Karin Greef (University of Cologne) and Gerd Welp and Addi Kiener (University of Bonn) for analyzing the extracts, and Ruth Bruker and Stefan Roitsch (University of Cologne) for EDX analysis. Additionally, we are grateful to the Duke of Croy and Thomas Seine, who enabled the field measurements.

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Authors and Affiliations

  1. Department Geowissenschaften, Bodengeographie/Bodenkunde, Universität zu Köln, Albertus-Magnus-Platz, 50923, Köln, Germany

    Kristof Dorau & Tim Mansfeldt

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  1. Kristof Dorau
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  2. Tim Mansfeldt
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Correspondence to Tim Mansfeldt.

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Responsible editor: Dong-Mei Zhou

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Dorau, K., Mansfeldt, T. Manganese and iron oxide-coated redox bars as a tool to in situ study the element sorption in wet soils. J Soils Sediments 16, 976–986 (2016). https://doi.org/10.1007/s11368-015-1300-6

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  • DOI: https://doi.org/10.1007/s11368-015-1300-6

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