Synchrotron-based X-ray study of iron oxide transformations in terraces from the Tinto-Odiel river system: Influence on arsenic mobility

Simultaneous analysis of micro-X-ray diffraction (μ-XRD) and micro-X-ray fluorescence (μ-XRF) based on synchrotron light sources, and electron microprobe (EMP) analyses, were performed on iron terrace samples taken from Tinto-Odiel river system from the Iberian Pyrite Belt (IBP, SW Iberian Peninsula). Iron terraces are formed during the oxidation and precipitation of dissolved iron along the riverbeds impacted by acid mine drainage (AMD). This paper includes the study of actively-forming current terraces and fossil terraces isolated from the stream courses due to the river migration over time. The results of the study of current terrace samples from AMD-affected streams of two IPB abandoned mines (Tinto Santa Rosa and Cueva de la Mora) showed that fresh precipitates at the surface are composed primarily of metastable schwertmannite, which is gradually transformed at depth over short-time scales into goethite. Sediments of ancient terraces are composed mainly of goethite, which most likely originated from the re-crystallization of a precursor schwertmannite. However, at century-time scale, goethite partially re-crystallizes to hematite due to diagenetic processes. The transformation rate of goethite into hematite is negatively correlated with grain size and the crystallinity of goethite. Moreover, this transformation is accompanied by an increase in grain size and a decrease in surface area of hematite, and a concomitant decrease in arsenic trapped in the solid. This increase in the arsenic mobility during the diagenetic maturation should be considered in the development of conceptual and analytical models describing long-term fate, transport and bioavailability of arsenic in environmental systems.