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FeS-Induced Radical Formation and Its Effect on Plasmid DNA

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Abstract

Plasmid DNA was incubated at 25°C with aqueous solutions of dissolved Fe(II), S(-II), and nanoparticulate FeS with a mackinawite structure, FeSm. At ≥0.1 mM total dissolved Fe(II) and S(-II), an increase in the proportion of the relaxed plasmid DNA occurs, through scission of the DNA backbone. In solutions where FeSm was precipitated, nanoparticulate FeSm binds to the DNA molecules. In solutions with concentrations below the FeSm solubility product, nicking of supercoiled pDNA occurs. Plasmid DNA appears to be a sensitive proxy for radical reactions. The reactant is proposed to be a sulfur-based radical produced from the iron-catalyzed decomposition of bisulfide, in a manner analogous to the Fenton reaction. This is further supported by experiments that suggest that sulfide free radicals are produced during the photolysis of aqueous solutions of polysulfides. Supercoiling of DNA affects nearly all DNA–protein transactions so the observation of relaxation of supercoiled forms through reaction with FeS solutions has direct implications to biochemistry. The results of this experimentation suggest that genotoxicity in FeS-rich systems is a further contributory factor to the limited survival of organisms in sulfidic environments. Mutations resulting from the interactions of organisms and mobile elements, such as plasmids, in sediments will also be affected in sulfide-rich environments.

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Acknowledgments

As with much else in modern aquatic geochemistry, this study was inspired by John Morse. John was struck by the way that many sulfide reactions in nature seemed to display similar attributes to classical radical reactions. During many conversations, we discussed ways in which this idea could be probed. The work was funded by a Charles Wright Scholarship to BH from Cardiff University and NERC grant NRE/L/S/2000/00611 to DR. We thank Professor A. Weightman for assistance in the DNA experimentation. Professor George Luther III made us aware of the MO data on sulfur and hydroxy radicals, and we appreciate his editorial contributions. We thank Professor Martin Schoonen and two anonymous referees for their comments, which did much to improve the original submission.

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Authors and Affiliations

  1. School of Earth and Ocean Sciences, Cardiff University, Cardiff, CF103YE, UK

    D. Rickard, B. Hatton & A. Oldroyd

  2. School of Chemistry, Cardiff University, Cardiff, CF103YE, UK

    D. M. Murphy

  3. School of Geosciences, University of Edinburgh, Edinburgh, EH9 3JW, UK

    I. B. Butler

  4. ECOSSE (Edinburgh Collaborative of Subsurface Science and Engineering), A joint research Institute of the Edinburgh Research Partnership in Engineering and Mathematics, Edinburgh, UK

    I. B. Butler

  5. School of Biosciences, Cardiff University, Cardiff, CF103YE, UK

    A. Hann

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  1. D. Rickard
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Correspondence to D. Rickard.

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Rickard, D., Hatton, B., Murphy, D.M. et al. FeS-Induced Radical Formation and Its Effect on Plasmid DNA. Aquat Geochem 17, 545–566 (2011). https://doi.org/10.1007/s10498-010-9116-x

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  • DOI: https://doi.org/10.1007/s10498-010-9116-x

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