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Hydrothermal vents as a kinetically stable source of iron-sulphide-bearing nanoparticles to the ocean

Abstract

Hydrothermal vents emit sulphur and metals to the ocean1. Particular attention has been paid to hydrothermal fluxes of iron2,3,4, a limiting micronutrient of marine primary production5. Vent-derived iron was previously thought to rapidly oxidize and precipitate around vents6. However, organic matter can bind to and stabilize dissolved and particulate iron in hydrothermal plumes7,8,9, facilitating its dispersion into the open ocean10. Here, we report measurements of the chemical speciation of sulphide and iron in high-temperature fluids emanating from vents in the East Pacific Rise and the Eastern Lau Spreading Center. We show that pyrite nanoparticles—composed of iron and sulphur—account for up to 10% of the filterable iron (less than 200 nm in size) in these fluids. We suggest that these particles form before the discharge of the vent fluid. We estimate that pyrite nanoparticles sink more slowly than larger plume particles, and are more resistant to oxidation than dissolved Fe(II) and FeS. We suggest that the discharge of iron in the form of pyrite nanoparticles increases the probability that vent-derived iron will be transported over long distances in the deep ocean.

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Figure 1: Sulphide speciation for the vent fluids.
Figure 2: Temperature of the vent versus the ratio CRS:ΔFe–N.
Figure 3: Pyrite nanoparticles as a previously unrecognized source of iron to the deep ocean.

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References

  1. German, C. R. & von Damm, K. L. Hydrothermal processes. Treatise Geochem. 6, 181–222 (2004).

    Google Scholar 

  2. Boyle, E. A. et al. Iron, manganese, and lead at Hawaii Ocean time-series station ALOHA: Temporal variability and an intermediate water hydrothermal plume. Geochim. Cosmochim. Acta 69, 933–952 (2005).

    Article  Google Scholar 

  3. Bennett, S. A. et al. The distribution and stabilization of dissolved Fe in deep-sea hydrothermal plumes. Earth Planet. Sci. Lett. 270, 157–167 (2008).

    Article  Google Scholar 

  4. Taglibue, A. et al. Hydrothermal contribution to the oceanic dissolved iron inventory. Nature Geosci. 3, 252–256 (2010).

    Article  Google Scholar 

  5. Boyd, P. W. et al. Mesoscale iron enrichment experiments 1993–2005: Synthesis and future directions. Science 315, 612–617 (2007).

    Article  Google Scholar 

  6. Mottl, M. J. & McConachy, T. F. Chemical processes in buoyant hydro-thermal plumes on the East Pacific Rise near 21° N. Geochim. Cosmochim. Acta 54, 1911–1927 (1990).

    Article  Google Scholar 

  7. Statham, P. J., German, C. R. & Connelly, D. P. Iron(II) distribution and oxidation kinetics in hydrothermal plumes at the Kairei and Edmond vent sites, Indian Ocean. Earth Planet. Sci. Lett. 236, 588–596 (2005).

    Article  Google Scholar 

  8. Schmidt, K., Koschinsky, A., Garbe-Schonberg, D., de Carvalho, L. M. & Seifert, R. Geochemistry of hydrothermal fluids from the ultramafic-hosted Logatchev hydrothermal field, 15° N on the Mid-Atlantic Ridge: Temporal and spatial investigation. Chem. Geol. 242, 1–21 (2007).

    Article  Google Scholar 

  9. Toner, B. M. et al. Preservation of iron (II) by carbon-rich matrices in a hydrothermal plume. Nature Geosci. 2, 197–201 (2009).

    Article  Google Scholar 

  10. Wu, J., Wells, M. L. & Remember, R. Dissolved iron anomaly in the deep tropical–subtropical Pacific: Evidence for long-range transport of hydrothermal iron. Geochim. Cosmochim. Acta 75, 460–468 (2011).

    Article  Google Scholar 

  11. Elderfield, H. & Schultz, A. Mid-ocean ridge hydrothermal fluxes and the chemical composition of the ocean. Annu. Rev. Earth Planet. Sci. 24, 191–224 (1996).

    Article  Google Scholar 

  12. Feely, R. A. et al. Composition and dissolution of black smoker particulates from active vents on the Juan de Fuca Ridge. J. Geophys. Res. 92, 11347–11363 (1987).

    Article  Google Scholar 

  13. Field, M. P. & Sherrell, R. M. Dissolved and particulate Fe in a hydrothermal plume at 9° 45′ N, East Pacific Rise: Slow Fe(II) oxidation kinetics in Pacific plumes. Geochim. Cosmochim. Acta 64, 619–628 (2000).

    Article  Google Scholar 

  14. Luther, G. W. et al. Chemical speciation drives hydrothermal vent ecology. Nature 410, 813–816 (2001).

    Article  Google Scholar 

  15. Hsu-Kim, H., Mullaugh, K. M., Tsang, J. J., Yucel, M. & Luther, G. W. Formation of Zn- and Fe-sulphides near hydrothermal vents at the Eastern Lau Spreading Center: Implications for sulphide bioavailability to chemoautotrophs. Geochem. Trans., 9, 6 (2008).

    Article  Google Scholar 

  16. Von Damm, K. L. in AGU Geophysical Monograph 144. The Subsurface Biosphere at Mid-Ocean Ridges (eds Wilcock, W. S. D., DeLong, E. F., Kelley, D. S., Baross, J. A. & Cary, S. C.) 245–268 (American Geophysical Union, 2004).

    Book  Google Scholar 

  17. Von Damm, K. L. et al. Chemistry of submarine hydrothermal solutions at 21° N, East Pacific Rise. Geochim. Cosmochim. Acta 49, 2197–2220 (1985).

    Article  Google Scholar 

  18. Fossing, H. & Jørgensen, B. B. Measurement of bacterial sulphate reduction in sediments: Evaluation of a single step chromium reduction method. Biogeochemistry 8, 205–222 (1989).

    Article  Google Scholar 

  19. Stookey, L. L. Ferrozine—a new spectrophotometric reagent for iron. Anal. Chem. 42, 779–781 (1970).

    Article  Google Scholar 

  20. Huerta-Diaz, M. A. & Morse, J. W. Pyritization of trace metals in anoxic marine sediments. Geochim. Cosmochim. Acta 56, 2681–2702 (1992).

    Article  Google Scholar 

  21. Vaughan, D. J. & Craig, J. R. Mineral Chemistry of Metal Sulphides (Cambridge Univ. Press, 1978).

    Google Scholar 

  22. Morse, J. W. & Luther, G. W. Chemical influences on trace metal-sulphide interactions in anoxic sediments. Geochim. Cosmochim. Acta 63, 3373–3378 (1999).

    Article  Google Scholar 

  23. Koski, R. A., Jonasson, R. I., Kadko, D., Smith, V. K. & Wong, F. L. Compositions, growth mechanisms, and temporal relations of hydrothermal sulphide–sulphate–silica chimneys at the northern Cleft segment, Juan de Fuca Ridge. J. Geophys. Res 99, 4813–4832 (1994).

    Article  Google Scholar 

  24. Tivey, M. K. The influence of hydrothermal fluid composition and advection rates on black smoker chimney mineralogy: Insights from modeling transport and reaction. Geochim. Cosmochim. Acta 59, 1933–1949 (1995).

    Article  Google Scholar 

  25. Rickard, D. T. Kinetics of pyrite formation by the H2S oxidation of iron (II) monosulphide in aqueous solutions between 25 and 125 °C: The rate equation. Geochim. Cosmochim. Acta 61, 115–134 (1997).

    Article  Google Scholar 

  26. Rickard, D. T. & Luther, G. W. Kinetics of pyrite formation by the H2S oxidation of iron (II) monosulphide in aqueous solutions between 25 and 125 °C: The mechanism. Geochim. Cosmochim. Acta 61, 135–147 (1997).

    Article  Google Scholar 

  27. Luther, G. W. & Rickard, D. T. Metal sulphide cluster complexes and their biogeochemical importance in the environment. J. Nanopart. Res. 7, 389–407 (2005).

    Article  Google Scholar 

  28. Mullaugh, K. M. & Luther, G. W. Growth kinetics and long-term stability of CdS nanoparticles in aqueous solution under ambient conditions. J. Nanopart. Res. 13, 393–404 (2011).

    Article  Google Scholar 

  29. Nicholson, R. V., Gillham, R. W. & Reardon, E. J. Pyrite oxidation in carbonate-buffered solution 2. Rate control by oxide coatings. Geochim. Cosmochim. Acta 54, 395–402 (1990).

    Article  Google Scholar 

  30. Feely, R. et al. Composition and sedimentation of hydrothermal plume particles from North Cleft segment, Juan de Fuca Ridge. J. Geophys. Res. 99, 4985–5006 (1994).

    Article  Google Scholar 

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Acknowledgements

This work was supported by grants to G.W.L. III from the National Science Foundation RIDGE program and the University of Delaware’s NSF EPSCoR program. A.G. acknowledges support from the Critical Zone research program funded by the University of Delaware. We thank E. Croker for assistance with SEM imaging, S. Modla for assistance with TEM imaging and C. Golt for assistance in ICP analyses.

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M.Y. and G.W.L. III designed the study. M.Y., A.G. and G.W.L. III performed sample collection and on-board processing. M.Y. performed sulphide and iron speciation analyses. A.G. performed other metal analyses and reaction kinetics calculations. C.S.C. performed TEM analysis of pyrite nanoparticles and contributed to data analysis. M.Y. and G.W.L. III drafted the manuscript. All authors contributed to interpretation of the results and editing of the manuscript.

Corresponding authors

Correspondence to Mustafa Yücel or George W. Luther III.

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The authors declare no competing financial interests.

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Yücel, M., Gartman, A., Chan, C. et al. Hydrothermal vents as a kinetically stable source of iron-sulphide-bearing nanoparticles to the ocean. Nature Geosci 4, 367–371 (2011). https://doi.org/10.1038/ngeo1148

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