Time-Resolved Investigation of Cobalt Oxidation by Mn(III)-Rich δ-MnO2 Using Quick X-ray Absorption Spectroscopy.

Manganese oxides are important environmental oxidants that control the fate of many organic and inorganic species including cobalt. We applied ex situ quick X-ray absorption spectroscopy (QXAS) to determine the time evolution of Co(II) and Co(III) surface loadings and their respective average surface speciation in Mn(III)-rich δ-MnO2 samples at pH 6.5 and loadings of 0.01-0.20 mol Co mol(-1) Mn. In this Mn oxide, which contained few unoccupied vacancies but abundant Mn(III) at edge and interlayer sites, Co(II) sorption and oxidation started at the particle edges. We found no evidence for Co(II) oxidation by interlayer Mn(III) or Mn(III, IV) adjacent to vacancy sites at <10 min. After 10 min, basal surface sites were implicated due to slow Co oxidation by interlayer Mn(III) and reactive sites formed upon removal of interlayer Mn(III), such that 50-60% of the sorbed Co was incorporated into the MnO2 sheets or adsorbed at vacancy sites by 12 h. Our findings indicate that the redox reactivity of surface sites depends on Mn valence and crystallographic location, with Mn(III) at the edges being the most effective oxidant at short reaction times and Mn(III,IV) in the MnO2 sheet contributing at longer reaction times.

Highly mobile iron pool from a dissolution-readsorption process.

Oxalate (C2O4 2-) acts synergistically on the dissolution of goethite (alpha-FeOOH) in the presence of siderophores that are secreted by plants and microorganisms to sequester iron. We report here the first in situ molecular-scale observations of synergistic ligand-promoted dissolution processes. We show that there are conditions under which oxalate promotes goethite dissolution, but dissolved Fe(III) concentrations do not increase because Fe(III)-oxalate complexes readsorb to the mineral surface. We demonstrate that these readsorbed Fe(III)-oxalate complexes are highly mobile, extremely reactive in the presence of uncomplexed siderophores, and responsible for the synergistic effects on the dissolution of goethite.