Uranium isotope fractionation during adsorption to Mn-oxyhydroxides

Environ Sci Technol. 2011 Feb 15;45(4):1370-5. doi: 10.1021/es103061v. Epub 2011 Jan 20.


Previous work has shown uranium (U) isotope fractionation between natural ferromanganese crusts and seawater. Understanding the mechanism that causes (238)U/(235)U fractionation during adsorption to ferromanganese oxides is a critical step in the utilization of (238)U/(235)U as a tracer of U adsorption reactions in groundwater as well as a potential marine paleoredox proxy. We conducted U adsorption experiments using synthetic K-birnessite and U-bearing solutions. These experiments revealed a fractionation matching that observed between seawater and natural ferromanganese sediments: adsorbed U is isotopically lighter by ∼0.2‰ (δ(238/235)U) than dissolved U. As the redox state of U does not change during adsorption, a difference in the coordination environment between dissolved and adsorbed U is likely responsible for this effect. To test this hypothesis, we analyzed U adsorbed to K-birnessite in our experimental study using extended X-ray absorption fine structure (EXAFS) spectroscopy, to obtain information about U coordination in the adsorbed complex. Comparison of our EXAFS spectra with those for aqueous U species reveals subtle, but important, differences in the U-O coordination shell between dissolved and adsorbed U. We hypothesize that these differences are responsible for the fractionation observed in our experiments as well as for some U isotope variations in nature.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Adsorption
  • Chemical Fractionation
  • Iron / chemistry
  • Manganese / chemistry
  • Oxidation-Reduction
  • Oxides / chemistry
  • Seawater / chemistry
  • Uranium / chemistry*
  • Water Pollutants, Radioactive / chemistry*


  • Oxides
  • Water Pollutants, Radioactive
  • birnessite
  • ferro-manganese alloy
  • Manganese
  • Uranium
  • Iron