Uranium isotope fractionation during adsorption to Mn-oxyhydroxides

Gregory A. Brennecka, Laura E. Wasylenki, John R. Bargar, Stefan Weyer, Ariel D. Anbar

Research output: Contribution to journalArticlepeer-review

156 Scopus citations


Previous work has shown uranium (U) isotope fractionation between natural ferromanganese crusts and seawater. Understanding the mechanism that causes 238U/235U fractionation during adsorption to ferromanganese oxides is a critical step in the utilization of 238U/235U 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‰ (δ238/235U) 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.

Original languageEnglish (US)
Pages (from-to)1370-1375
Number of pages6
JournalEnvironmental Science and Technology
Issue number4
StatePublished - Feb 15 2011
Externally publishedYes

ASJC Scopus subject areas

  • General Chemistry
  • Environmental Chemistry


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