Contaminant mobilization by metallic copper and metal sulphide colloids in flooded soil

Abstract

Colloids, such as submicrometre mineral particles or bacterial cells, can act as carriers enhancing the mobility of poorly soluble contaminants in subsurface environments1,2. In sulphate-reducing soils and sediments, metal sulphide precipitation has been proposed3,4,5,6 to generate contaminant-bearing sulphide colloids, which could transport contaminants traditionally thought to be immobilized by metal sulphide formation7. However, direct evidence for such a process is lacking. Here, we report the composition and morphology of pore-water colloids formed in contaminated floodplain soil when flooded with synthetic river water over a four-week period. We show that, on flooding, bacteria dispersed in the pore water mobilize copper by inducing biomineralization of metallic copper(0). We suggest that copper(0) crystals form by disproportionation of copper(I), which is released by copper-stressed bacteria to maintain copper homeostasis8,9. Sulphate reduction, which started on the fourth day of flooding, resulted in the mobilization of cadmium and lead, which were partitioned to copper-rich sulphide colloids showing two types of morphology: bacterium-associated 50–150-nm-diameter hollow particles formed through copper(0) transformation, and dispersed <50 nm nanoparticles, probably formed through homogeneous precipitation. The slow deposition of both types of sulphide colloid ensured elevated contaminant concentrations in the pore water for weeks. Our findings imply that colloid formation can enhance contaminant release from periodically sulphate-reducing soils and sediments, potentially polluting surface- and groundwaters.

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Figure 1: Temporal dynamics of the pore-water composition during flooding.
Figure 2: Temporal evolution of Cu speciation.
Figure 3: Temporal evolution of colloid morphology and composition.
Figure 4: Inhibitors of Cu(0) biomineralization.

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Acknowledgements

We thank K. Barmettler for support in the laboratory, S. Mangold for assistance at the XAS beamline at ANKA, and U. Skyllberg and J. F. W. Mosselmans for sharing reference XAS spectra. We thank ANKA Angströmquelle Karlsruhe GmbH, Germany, for allocation of synchrotron beamtime and acknowledge the support of the Electron Microscopy Centre (EMEZ) of ETH Zurich, Switzerland. Funding from the Swiss State Secretariat for Education and Research (contract 03.0353-1) as a contribution to the EU project AquaTerra is acknowledged.

Author information

F.-A.W. designed and performed all experiments and measurements, evaluated the results and wrote the manuscript as part of his PhD thesis. A.V. conducted EXAFS analyses and contributed to writing. R.Ka. conducted TEM analyses. A.V. and R.Kr. initiated and supervised the project. All authors discussed the results and commented on the manuscript.

Correspondence to Andreas Voegelin.

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Weber, F., Voegelin, A., Kaegi, R. et al. Contaminant mobilization by metallic copper and metal sulphide colloids in flooded soil. Nature Geosci 2, 267–271 (2009). https://doi.org/10.1038/ngeo476

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