Zinc isotope fractionation during adsorption onto Mn oxyhydroxide at low and high ionic strength

Marine ferromanganese sediments represent one of the largest sinks from global seawater for Zn, a critical trace metal nutrient. These sediments are variably enriched in heavier isotopes of Zn relative to deep seawater, and some are among the heaviest natural samples analyzed to date. New experimental results demonstrate that adsorption of Zn to poorly crystalline Mn oxyhydroxide results in preferential association of heavier isotopes with the sorbent phase. At low ionic strength our experimental system displayed a short-lived kinetic isotope effect, with light isotopes adsorbed to birnessite (Delta(66/64) Zna(dsorbed-dissolved) similar to -0.2 parts per thousand). After 100 h the sense of fractionation was opposite, such that heavier isotopes were preferentially adsorbed at steady state, but the magnitude of Delta(66/64) Znadsorbed-dissolved was indistinguishable from zero (+ 0.05 +/- 0.08 parts per thousand). At high ionic strength, we observed preferential sorption of heavy isotopes, with a strong negative correlation between Delta(66/64) Znadsorbed-dissolved and the percentage of Zn on the birnessite. Values of Delta(66/64) Znadsorbed-dissolved ranged from nearly +3 parts per thousand at low surface loading to +0.16 parts per thousand at high surface loading. Based on previous EXAFS work we infer that Zn adsorbs first as tetrahedral, inner-sphere complexes at low surface loading, with preferential incorporation of heavier isotopes relative to the octahedral Zn species predominating in solution. As surface loading increases, so does the proportion of Zn adsorbing as octahedral complexes, thus diminishing the magnitude of fractionation between the dissolved and adsorbed pools of Zn. The magnitude of fractionation at high ionic strength is also governed by aqueous speciation of Zn in synthetic seawater; a substantial fraction of Zn ions reside in chloro complexes, which preferentially incorporate light Zn isotopes, and this drives the adsorbed pool to be heavier relative to the bulk solution than it was at low ionic strength. Our results explain the observation that ferromanganese sediments are enriched in heavier isotopes of Zn relative to deep seawater. This represents a step towards building a robust mass balance model for Zn isotopes in the oceans and potentially using Zn isotopes to trace biogeochemical cycling of this important element in the modern and ancient oceans. (C) 2015 Elsevier Ltd. All rights reserved.