Trace element-mineral associations in modern and ancient iron terraces in acid drainage environments

•Geochemistry and mineralogy of ancient and modern Fe terraces were examined.•Schwertmannite transformed to goethite with depth in modern terraces.•Hematite and highly crystalline goethite were observed in ancient terraces.•Trace element affinity followed order: schwertmannite ≥ goethite > hematite.•Recrystallization of Fe-precipitates could potentially release trace elements at long-term.

Iron-rich sediments commonly cover riverbeds that have been affected by acid drainage associated with sulfide-mineral oxidation. Freshly-formed precipitates correspond to poorly-crystalline oxyhydroxysulfates that recrystallize over time. This study examined the distribution and mineral association of trace elements (e.g., As, Cu, Zn) in modern and ancient (~ 6 Ma) Fe terraces in the Tinto river basin, Spain. The mineral composition of the terraces was determined by Raman μ-spectroscopy. Chemical digestions, electron probe microanalyses, and synchrotron-based μ-X-ray fluorescence mapping were used to examine As, Cu, and Zn distribution and corresponding mineral associations. Fresh precipitates at modern terrace surfaces were dominated by schwertmannite, which contained high As, Cu, Mn, and Zn concentrations. However, schwertmannite transforms into goethite over days to weeks in the deeper part of the current terraces and into hematite over centuries. Affinity for trace elements was generally highest for schwertmannite and lowest for hematite, which suggests that their retention by Fe terraces decreases during mineral transformation. Hence, schwertmannite acts as temporary sink for contaminants, which are again released over long time periods. These findings should be considered for management and treatment of possible water resources affected by acid mine drainage.

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