Villinski John E, Saiers James E, Conklin Martha H
Department of Hydrology and Water Resources, The University of Arizona, P.O. Box 210011, Tucson, Arizona 85721-0011, USA.
Environ Sci Technol. 2003 Dec 15;37(24):5589-96. doi: 10.1021/es034060r.
We conducted batch-reactor experiments to measure the reductive dissolution of pyrolusite-coated (beta-MnO2) quartz by Fe(II) under conditions representative of an acid mine-drainage subsurface plume. The results reveal that reductive dissolution rates were initially rapid but declined considerably as Fe(III)(aq), a product of the reductive-dissolution reaction, was removed from solution by heterogeneous precipitation. The inhibition of reductive-dissolution was attributed to blocking of the beta-MnO2 surface sites by the Fe(III)(s) precipitate. Calculations of a simple model that accounts for the effects of Fe(III)(s) precipitate formation on reductive dissolution rates closely match temporal changes in Mn(II), Fe(II), and Fe(II) concentrations measured in 10 experiments, distinguished on the basis of the initial Fe(II)-to-Mn(IV) mole ratio and the initial Fe(III)(aq) concentration. The model-data comparisons reveal that the initial reaction rate on a clean beta-MnO2 surface exceeds the long-term reaction rate by 3 orders of magnitude, highlighting the importance of linking Fe(III) precipitation with the reductive dissolution of beta-MnO2 by Fe(II).
