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The Influence of Redox Reactions on the Uptake of Dissolved Ce by Suspended Fe and Mn Oxide Particles

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Abstract

Laboratory experiments were conducted to evaluate the partitioning ofrare earth elements (REE) between solution and suspended particles. Becauseof their strong tendency to complex, the REE can be used to study a varietyof marine processes and in particular particle scavenging. In this study, anemphasis was placed on examining abiotic redox processes that influence theuptake of dissolved Ce by particles. Batch sorption experiments wereconducted with REE and synthetic mineral phases over the range of pH4–9. The solutions varied in ionic strength between 0 and 0.7 M andconsisted of individual solutes (NaNO3, NaCl, andNa2SO4), ionic mixtures that duplicate theseawater composition, and natural seawater. The uptake of REE from solutionwas also studied at a Pt electrode coated with \(\delta {\text{ - MnO}}_{\text{2}} \)using cyclic voltametry.

Experimental results are consistent with uptake of dissolved Ce onto\(\delta {\text{ - MnO}}_{\text{2}} \) occurring by a combination of oxidativescavenging and surface complexation. The contribution of oxidativescavenging to the removal of Ce from solution is most pronounced at acidicpH, where the strictly trivalent REE exhibit little propensity for sorptiononto \(\delta {\text{ - MnO}}_{\text{2}} \). Sorption of dissolved Ce onto FeOOH occursin a manner analogous to that of the other strictly trivalent REE and nocontribution from oxidative scavenging is observed on this mineral phase atlow pH. Our work also substantiates the hypothesis that anions in solution,particularly \({\text{SO}}_{\text{4}}^{{\text{2}} - } \) and Cl-, aswell as those adsorbed on the surface of the particles, influence the extentof Ce uptake by \(\delta {\text{ - MnO}}_{\text{2}} \).

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References

  • Aplin, A. C. (1984) Rare earth element geochemistry of Central Pacific manganese encrustations. Earth and Planet. Sci. Lett. 71, 13–22.

    Article  Google Scholar 

  • Atkinson, R. J., Posner, A. M. and Quirk, J. P. (1967) Adsorption of Potential Ions at the Ferric Oxide Aqueous Electrolyte Interface. J. Phys. Chem. 71, 550–558.

    Article  Google Scholar 

  • Baes, C. F. and Mesmer, R. E. (1976) The Hydrolysis of Cations. John Wiley and Sons, 489 pp.

  • Bau, M., Koschinsky, A. Dulski, P. and Hein, J. R. (1996) Comparison of the partitioning behaviour of yttrium, rare elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater. Geochim. Cosmochim. Acta 60, 1709–1725.

    Article  Google Scholar 

  • Byrne, R. H. and Kim, K. H. (1990) Rare earth element scavenging in seawater. Geochim. Cosmochim. Acta 54, 2645–2656.

    Article  Google Scholar 

  • Cantrell J. and Byrne R. H. (1987) Rare earth element complexation by carbonate and oxalate ions. Geochim. Cosmochim. Acta 51, 597–605.

    Article  Google Scholar 

  • Davis, J. A. and Leckie, J. O. (1978) Surface ionization and complexation at the oxide/water interface. II: Surface properties of amorphous iron oxyhydroxide and adsorption of metal ions. J. Colloid. Interface Sci. 67, 90–107.

    Article  Google Scholar 

  • De Baar, H. J. W., Bacon, M. P., Brewer, P. G. and Bruland, K. W. (1985) Rare earth elements in the Pacific and Atlantic Oceans. Geochim. Cosmochim. Acta 49, 1943–1959.

    Article  Google Scholar 

  • De Carlo, E. H. (1991) Paleoceanographic implications of rare earth element variability within a Fe-Mn crust from the central Pacific Ocean. Mar. Geol. 98(2/4), 449–467.

    Article  Google Scholar 

  • De Carlo, E. H. and Koeppenkastrop D. (1991) Sampling and methods of characterization of surface reactivity. in: Marine Particles: Analysis and Characterization, Geophysical Monograph 63 (eds. D. C. Hurd and D. W. Spencer), American Geophysical Union, pp. 419–427.

  • De Carlo, E. H. and McMurtry, G. M. (1992) Rare earth element geochemistry of ferromanganese crusts from the Hawaiian Archipelago. Chem. Geol. 95, 235–250.

    Article  Google Scholar 

  • De Carlo, E. H., McMurtry, G. M. and Kim, K. H., (1987) Geochemistry of ferromanganese crusts from the Hawaiian Archipelago-I. Northern survey areas. Deep-Sea Research 34: 441–467.

    Article  Google Scholar 

  • De Carlo, E. H., Wen, X. Y, and Cowen, J. P. (1998) Rare earth element fractionation in hydrogenetic Fe-Mn crusts: The influence of carbonate complexation and phosphatization on Sm/Yb ratios, in: SEPM Special Volume: Marine Authigenisis, from Global to Microbial (eds. C. Glenn and W. C. Burnett), In press.

  • Dzombak, D. A. and Morel, F. M. M. (1990) Surface Complexation Modeling: Hydrous Ferric Oxide. John Wiley and Sons, New York.

    Google Scholar 

  • Elderfield, H. and Greaves, M. J. (1982) The rare earth elements in seawater. Nature 296, 214–219.

    Article  Google Scholar 

  • Elderfield, H., (1988) The oceanic chemistry of the rare earth elements. Phil. Trans. R. Soc. Lond. A 325, 105–126.

    Google Scholar 

  • Elderfield, H., Upstill-Goddard, R. and Sholkovitz, E. R. (1990) The rare earth elements in rivers, estuaries, and coastal seas and their significance to the composition of seawater. Geochim. Cosmochim. Acta 54, 971–991.

    Article  Google Scholar 

  • Erel, Y. and Morgan, J. J. (1991) The effect of surface reactions on the relative abundance of trace metals in deep-ocean water. Geochim. Cosmochim. Acta 55, 1807–1813.

    Article  Google Scholar 

  • Erel, Y. and Stolper, M. (1993) Modeling of rare-earth element partitioning between particles and solution in aquatic environments. Geochim. Cosmochim. Acta, 57, 513–518.

    Article  Google Scholar 

  • German, C. R. and Elderfield, H. (1990) Application of the Ce anomaly as a paleoredox indicator: The ground rules. Paleoceanography 5: 823–833.

    Article  Google Scholar 

  • German, C. R., Holliday, B. P., and Elderfield, H. (1991) Redox cycling of the rare earth elements in the suboxic zone of the Black Sea. Geochim. Cosmochim. Acta, 55, 3553–3558.

    Article  Google Scholar 

  • German, C. R., Masuzawa, T., Greaves, M. J., Elderfield, H. and Edmond, J. M. (1995) Dissolved rare earth elements in the Southern Ocean: Cerium oxidation and the influence of hydrography. Geochim. Cosmochim. Acta 59, 1551–1558.

    Article  Google Scholar 

  • Goldberg, E. D. (1961) Chemistry of the oceans, in: Oceanography (ed M. Sears), 67, 538–597, Am. Assoc. Ad. Sci. Publ.

  • Goldberg, E. D., Koide, M., Schmitt, R. A. and Smith, R. H. (1963) Rare earth distribution in the marine environment, J. Geophys. Res. 68, 4009–4217.

    Google Scholar 

  • Hein, J. R., Schwab, W. C. and Davis, A. S. (1988) Cobalt-and platinum-rich ferromanganese crusts and associated substrate rocks from the Marshall Islands. Mar. Geol. 78, 255–283.

    Article  Google Scholar 

  • Henderson P. (1984) General geochemical properties and abundances of the rare earth elements, in: Rare Earth Element Geochemistry (ed. P. Henderson), Elsevier Publishing, Amsterdam, pp. 1–32.

    Google Scholar 

  • Honeyman, B. D. and Santschi, P. H. (1989) A Brownian-pumping model for oceanic trace metal scavenging: Evidence from Th isotopes. J. Marine Research 47, 951–992.

    Google Scholar 

  • Hunter, K. A. (1991) Surface charge and size spectra of marine particles, in: Marine Particles: Analysis and Characterization (eds. D. C. Hurd and D. W. Spencer), Geophysical Monograph 63, American Geophysical Union, pp. 259–262.

  • Koeppenkastrop, D. (1992) Thermodynamic and Kinetic Studies on the Interaction of Rare Earth Elements with Metal Oxides. Unpublished Ph.D. Dissertation, University of Hawaii at Manoa, Honolulu, Hawaii, 409 pp.

  • Koeppenkastrop, D. and De Carlo, E. H. (1992) Sorption of rare earth elements from seawater onto pure mineral phases: An experimental approach. Chem. Geol. 95, 251–263.

    Article  Google Scholar 

  • Koeppenkastrop, D. and De Carlo, E. H. (1993) Uptake of rare earth elements from solution by metal oxides. Env. Sci. and Tech. 27, 1796–1802.

    Article  Google Scholar 

  • Koeppenkastrop, D., De Carlo, E. H. and Roth, M. (1991) A method to investigate the interaction of rare earth elements with metal oxides in aqueous solution. J. Radioanal. Nucl. Chem. 151(2), 337–346.

    Article  Google Scholar 

  • Lee, J. A., Maskell, W. C. and Tye, F. L. (1977) The electrochemical reduction of manganese dioxide in acidic solutions. J. Electroanal. Chem. 79, 79–104.

    Google Scholar 

  • Llompart, S., Ouboumour, H. and Yu, L. T. (1991) Oxygen regeneration of discharged manganese dioxide electrode. J. Electrochem. Soc. 138(3), 665–669.

    Article  Google Scholar 

  • Millero, F. J. (1985) The effect of ionic interactions on the oxidation of metals in natural waters. Geochim. Cosmochim. Acta. 49, 547–554.

    Article  Google Scholar 

  • Moffet, J. W. (1990) Microbially mediated cerium oxidation in seawater. Nature 345, 421–423.

    Article  Google Scholar 

  • Moffett, J. (1994). A radiotracer study of cerium and manganese uptake onto suspended particles in Chesapeake Bay. Geochim. Cosmochim. Acta 58, 695–703.

    Article  Google Scholar 

  • Murray, J. W. (1974) The surface chemistry of hydrous manganese dioxide, J. Coll. Interface Sci. 46, 357–371.

    Article  Google Scholar 

  • Nzikou, J. M., Aurousseau, M. and Lapicque, F. (1995) Electrochemical investigations of the Ce(III)/Ce(IV) couple related to a Ce(IV)-assisted process for SO2/NOx abatement. J. of Applied Electrochemistry. 25, 967–972.

    Google Scholar 

  • Parks, G. A. (1965) The isoelectric points of solid oxides, solid hydroxides, and aqueous hydroxo complex systems, Chem. Rev. 65, 177–198.

    Article  Google Scholar 

  • Piepgras, D. J. and Jacobsen, S. B. (1992) The behavior of rare earth elements in seawater: Precise determination of variations in the North Pacific water column. Geochim. Cosmochim. Acta. 56, 1851–1862.

    Article  Google Scholar 

  • Piper, D. Z. (1974) Rare earth elements in ferromanganese nodules and other marine phases. Geochim. Cosmochim. Acta 38, 1007–1022.

    Article  Google Scholar 

  • Randle, T. H. and Kuhn, A. T. (1983) Kinetics and mechanism of the Ce(IV)/Ce(III) redox reaction on a platinum electrode. J. Chem. Soc., Faraday Trans. 1 79, 1741–1756.

    Article  Google Scholar 

  • Schijf, J., de Baar, H. J. W. and Millero, F. J. (1994) Kinetics of Ce scavenging in the Black Sea. Mar. Chem. 46, 345.

    Article  Google Scholar 

  • Sholkovitz, E. R., Landing, W. M. and Lewis, B. L. (1994) Ocean particle chemistry: The fractionation of rare earth elements between suspended particles and seawater. Geochim. Cosmochim. Acta. 58, 1567–1579.

    Article  Google Scholar 

  • Smith, R. M. and Martell, A. E. (1976) Critical Stability Constants, Inorganic Complexes, Vol. 4. Plenum Press, N.Y.

    Google Scholar 

  • Tipping, E. and Cooke, D. (1982) The effects of adsorbed humic substances on the surface charge of goethite (α-FeOOH) in freshwaters, Geochim. Cosmochim. Acta 46, 75–80.

    Article  Google Scholar 

  • Wehrli, B., Sulzberger, B. and Stumm, W. (1989) Redox processes catalyzed by hydrous oxide surfaces. Chem. Geol. 78, 167–179.

    Article  Google Scholar 

  • Wen, X. Y., De Carlo, E. H. and Li, Y. H. (1997) Interelement relationships in ferromanganese crusts from the central Pacific Ocean: Their implications for crust genesis. Marine Geology 136(3/4), 277–297.

    Article  Google Scholar 

  • Wood, S. A. (1990) The aqueous geochemistry of the rare earth elements and yttrium. Part 1: Review of available low temperature data for inorganic complexes and the inorganic REE speciation of natural waters. Chem. Geol. 82(1/2), 159–186.

    Article  Google Scholar 

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Authors and Affiliations

  1. Department of Oceanography, SOEST, University of Hawaii, 1000 Pope Road, Honolulu, Hawaii, 96822

    Eric Heinen De Carlo & Xi-Yuan Wen

  2. Department of Chemistry, University of Hawaii, 2545 The Mall, Honolulu, Hawaii, 96822

    Mark Irving

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  1. Eric Heinen De Carlo
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  2. Xi-Yuan Wen
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De Carlo, E.H., Wen, XY. & Irving, M. The Influence of Redox Reactions on the Uptake of Dissolved Ce by Suspended Fe and Mn Oxide Particles. Aquatic Geochemistry 3, 357–389 (1997). https://doi.org/10.1023/A:1009664626181

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