Molybdenum isotope fractionation during adsorption by manganese oxides

J. Barling, Ariel Anbar

Research output: Contribution to journalArticle

222 Citations (Scopus)

Abstract

The isotopic composition of Mo (δ97/95Mo) in seawater is ∼2‰ heavier than Mo in marine ferromanganese crusts and nodules [Barling et al., Earth Planet. Sci. Lett. 193 (2001) 447-457; Siebert et al., Earth Planet. Sci. Lett. 211 (2003) 159-171]. To explore this phenomenon, we have conducted an experimental investigation into the mass-dependent fractionation of Mo isotopes during adsorption onto Mn oxyhydroxide. Two series of experiments were carried out: a 'time series', in which adsorption proceeded for 2-96 h; and a 'pH series' in which pH varied from 6.5 to 8.5. The extent of Mo adsorption by Mn oxyhydroxides decreases with increasing pH, a trend typical of anion adsorption, and takes 48 h to reach steady-state. Lighter Mo isotopes are preferentially adsorbed. Experimentally determined fractionation factors (α soln-MnOx) exhibit no systematic variation with either time or experimental pH. The mean α soln-MnOx for all experiments is 1.0018±0.0005 (2 S.D.). Comparison of the Mo isotopic data for experimental solutions and Mo adsorbed to Mn oxyhydroxide with predictions for 'closed system' equilibrium and Rayleigh fractionation models indicates that isotope fractionation occurs as a result of 'closed system' equilibrium exchange between dissolved and adsorbed Mo. The isotopic offset between dissolved and adsorbed Mo is comparable to that observed between Mo in seawater and Mo in ferromanganese nodules and crusts. It is therefore likely that adsorption of Mo to Mn oxyhydroxides is a significant factor in the fractionation of Mo isotopes in the oceans.

Original languageEnglish (US)
Pages (from-to)315-329
Number of pages15
JournalEarth and Planetary Science Letters
Volume217
Issue number3-4
DOIs
StatePublished - Jan 15 2004
Externally publishedYes

Fingerprint

molybdenum isotopes
Molybdenum
manganese oxides
manganese oxide
Fractionation
molybdenum
fractionation
Isotopes
isotope
adsorption
Adsorption
isotopes
nodules
Planets
Seawater
crusts
planet
Earth (planet)
crust
ferromanganese deposit

Keywords

  • Adsorption
  • Isotope fractionation
  • Manganese oxides
  • Molybdenum isotopes

ASJC Scopus subject areas

  • Geochemistry and Petrology
  • Geophysics

Cite this

Molybdenum isotope fractionation during adsorption by manganese oxides. / Barling, J.; Anbar, Ariel.

In: Earth and Planetary Science Letters, Vol. 217, No. 3-4, 15.01.2004, p. 315-329.

Research output: Contribution to journalArticle

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AB - The isotopic composition of Mo (δ97/95Mo) in seawater is ∼2‰ heavier than Mo in marine ferromanganese crusts and nodules [Barling et al., Earth Planet. Sci. Lett. 193 (2001) 447-457; Siebert et al., Earth Planet. Sci. Lett. 211 (2003) 159-171]. To explore this phenomenon, we have conducted an experimental investigation into the mass-dependent fractionation of Mo isotopes during adsorption onto Mn oxyhydroxide. Two series of experiments were carried out: a 'time series', in which adsorption proceeded for 2-96 h; and a 'pH series' in which pH varied from 6.5 to 8.5. The extent of Mo adsorption by Mn oxyhydroxides decreases with increasing pH, a trend typical of anion adsorption, and takes 48 h to reach steady-state. Lighter Mo isotopes are preferentially adsorbed. Experimentally determined fractionation factors (α soln-MnOx) exhibit no systematic variation with either time or experimental pH. The mean α soln-MnOx for all experiments is 1.0018±0.0005 (2 S.D.). Comparison of the Mo isotopic data for experimental solutions and Mo adsorbed to Mn oxyhydroxide with predictions for 'closed system' equilibrium and Rayleigh fractionation models indicates that isotope fractionation occurs as a result of 'closed system' equilibrium exchange between dissolved and adsorbed Mo. The isotopic offset between dissolved and adsorbed Mo is comparable to that observed between Mo in seawater and Mo in ferromanganese nodules and crusts. It is therefore likely that adsorption of Mo to Mn oxyhydroxides is a significant factor in the fractionation of Mo isotopes in the oceans.

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