Cu Binding to Iron Oxide-Organic Matter Coprecipitates in Solid and Dissolved Phases

Abstract:

Recent studies indicate that Cu is released from wetlands following storm events. Assymetrical field flow field fractionation (AF4) analyses as well as total and dissolved metal concentration measurements suggest iron oxide-organic matter complexes control Cu retention and release. Coprecipitation products of Fe oxide and organic matter were prepared under conditions similar to the wetland to assess Cu partitioning to and availability from solid phases that settle from solution as well as phases remaining suspended. Cu coprecipitation and sorption to organomineral precipitation solids formed at different Fe:organic carbon (OC) ratios were compared for net Cu removal and extractability. As more humic acid was present during precipitation of Fe, TEM images indicated smaller Fe oxide particles formed within an organic matrix as expected. In coprecipitation reactions, as the ratio of Fe:OC decreased, more Cu was removed from solution at pH 5.5 and below. However, in sorption reactions, there was an inhibition of Cu removal at low OC concentrations. As the pH increased from 5.5 to 7 and as solution phase OC concentration increased, more Cu remained dissolved in both coprecipitation and sorption reactions. The addition of Ca²⁺, glycine, histidine and citric acid or lowering the pH resulted in more extractable Cu from the coprecipitation compared with the sorption reactions. The variations in Cu extraction were likely due to a combination of a more amorphous structure in CPT products, and the relative abundance of available Fe oxide or OC binding sites. Suspended Fe oxide-organic matter coprecipitates were assessed using AF4 coupled to online TOC analysis and ICP-MS. In laboratory prepared samples, Cu was observed in a mixture of small 1-5 nm colloids of Fe oxide-organic matter precipitates, but the majority was observed in larger organic matter colloids and were not UV absorbing, suggesting more aliphatic carbon materials. In field samples, up to 60% of the dissolved Cu was associated with 1-5 nm colloids of mixed Fe oxide-organic matter precipitates. This research has implications for the assumption of additivity in binding phases and for researchers conducting binding or exposure experiments where metal speciation and lability control bioavailability and toxicity.