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Influence of pH on the redox chemistry of metal (hydr)oxides and organic matter in paddy soils

  • Soils, Sec 3 • Remediation and management of contaminated or degraded lands • Research Article
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Abstract

Purpose

The primary purpose of this study was to determine how flooding and draining cycles affect the redox chemistry of metal (hydr)oxides and organic matter in paddy soils and how the pH influences these processes. Our secondary purpose was to determine to what extent a geochemical thermodynamic equilibrium model can be used to predict the solubility of Mn and Fe during flooding and draining cycles in paddy soils.

Material and methods

We performed a carefully designed column experiment with two paddy soils with similar soil properties but contrasting pH. We monitored the redox potential (Eh) continuously and took soil solution samples regularly at four depths along the soil profile during two successive flooding and drainage cycles. To determine dominant mineral phases of Mn and Fe under equilibrium conditions, stability diagrams of Mn and Fe were constructed as a function of Eh and pH. Geochemical equilibrium model calculations were performed to identify Mn and Fe solubility-controlling minerals and to compare predicted total dissolved concentrations with their measured values.

Results and discussion

Flooding led to strong Eh gradients in the columns of both soils. In the acidic soil, pH increased with decreasing Eh and vice versa, whereas pH in the alkaline soil was buffered by CaCO3. In the acidic soil, Mn and Fe solubility increased during flooding due to reductive dissolution of their (hydr)oxides and decreased during drainage because of re-oxidation. In the alkaline soil, Mn and Fe solubility did not increase during flooding due to Mn(II) and Fe(II) precipitation as MnCO3, FeCO3, and FeS. The predicted levels of soluble Mn and Fe in the acidic soil were much higher than their measured values, but predictions and measurements were rather similar in the alkaline soil. This difference is likely due to kinetically limited reductive dissolution of Mn and Fe (hydr)oxides in the acidic soil. During flooding, the solubility of dissolved organic matter increased in both soils, probably because of reductive dissolution of Fe (hydr)oxides and the observed increase in pH.

Conclusions

Under alternating flooding and draining conditions, the pH greatly affected Mn and Fe solubility via influencing either reductive dissolution or carbonate formation. Comparison between measurements and geochemical equilibrium model predictions revealed that reductive dissolution of Mn and Fe (hydr)oxides was kinetically limited in the acidic soil. Therefore, when applying such models to systems with changing redox conditions, such rate-limiting reactions should be parameterized and implemented to enable more accurate predictions of Mn and Fe solubility.

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Acknowledgments

This research was financially supported by the CAS-KNAW Joint PhD Training Programme (no. 5237829), the Key Project of the National Natural Science Foundation of China (no. 40971250), and the Key Project of the National Natural Science Foundation of China (no. 41230858). This research is also part of the strategic research program KBIV—“Sustainable spatial development of ecosystems, landscapes, seas and regions,” which is funded by the Dutch Ministry of Economic Affairs. Dr. Hans Meeussen is gratefully acknowledged for his advice in constructing the Eh-pH diagrams with the ORCHESTRA modeling framework.

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Authors and Affiliations

  1. Department of Soil Quality, Wageningen University and Research Center (WUR), P.O. Box 47, 6700, Wageningen, The Netherlands

    Yunyu Pan, Gerwin F. Koopmans, Erwin J. M. Temminghoff & Rob N. J. Comans

  2. Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing, 210008, People’s Republic of China

    Yunyu Pan & Jing Song

  3. Alterra, WUR, P.O. Box 47, 6700, Wageningen, The Netherlands

    Luc T. C. Bonten

  4. Yantai Institute of Costal Zone Research, Chinese Academy of Sciences, Yantai, 264003, People’s Republic of China

    Yongming Luo

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  1. Yunyu Pan
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  2. Gerwin F. Koopmans
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  3. Luc T. C. Bonten
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  4. Jing Song
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Correspondence to Gerwin F. Koopmans.

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Pan, Y., Koopmans, G.F., Bonten, L.T.C. et al. Influence of pH on the redox chemistry of metal (hydr)oxides and organic matter in paddy soils. J Soils Sediments 14, 1713–1726 (2014). https://doi.org/10.1007/s11368-014-0919-z

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