TY - JOUR

T1 - Uranium isotope fractionation during adsorption to Mn-oxyhydroxides

AU - Brennecka, Gregory A.

AU - Wasylenki, Laura E.

AU - Bargar, John R.

AU - Weyer, Stefan

AU - Anbar, Ariel D.

PY - 2011/2/15

Y1 - 2011/2/15

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=79951667925&partnerID=8YFLogxK

U2 - 10.1021/es103061v

DO - 10.1021/es103061v

M3 - Article

C2 - 21250673

AN - SCOPUS:79951667925

VL - 45

SP - 1370

EP - 1375

JO - Environmental Science and Technology

JF - Environmental Science and Technology

SN - 0013-936X

IS - 4

ER -