Iron and Manganese Oxidation States, Bonding Environments, and Mobility in the Mining-Impacted Sediments of Coeur d’Alene Lake, Idaho: Core Experiments

Abstract

The mobility of a metal in mining-impacted sediments is determined by the environmental conditions that influence the metal’s oxidation state and bonding environment. Coeur d’Alene Lake, USA, has been impacted by legacy mining practices that allowed the hydrologic transport of mining waste to the lakebed, resulting in substantial amounts of redox-sensitive Fe and Mn along with Ag, As, Cd, Cu, Hg, Pb, Sb, and Zn. Future lake conditions may include algal blooms and additional algal detritus at the sediment–water interface, which may alter Fe and Mn forms that can influence their, and other metal(loid)s, mobility during seasonal anoxia. Cores of the lakebed sediments were exposed to anoxic and anoxic + algal detritus conditions for 8 weeks. Sediment samples were collected biweekly for analysis of Fe and Mn oxidation states and bonding environments by synchrotron-based X-ray absorption spectroscopy. Over the 8-week period and at a location 12.5 cm deep in the sediments, anoxic and anoxic + algae conditions produced limited changes in Fe and Mn oxidation states and bonding environments. At a location 2.5 cm below the sediment–water interface, the anoxic condition promoted a relatively stable environment in which Fe and Mn oxidation states and bonding environments did not vary greatly during the experiment. At the 2.5 cm depth, the anoxic + algae condition substantially altered the Mn oxidation state distribution and bonding environment, but this condition did not strongly influence the Fe oxidation state distribution or bonding environment. The anoxic + algae condition increased the presence of Mn3+, produced Mn4+ at select times, altered the Mn bonding environment, and temporarily increased the release of Mn into porewater. The algae influence on sediment and porewater Mn likely occurred because of the increased formation of organo-Mn complexes produced during algae-enhanced enzymatic processes. The lack of influence of algal detritus on sediment and porewater Fe and the formation of soluble organo-Mn complexes may limit the potential increase in the mobility of other metal(loid)s with future lake conditions.