Origin of the anomalies in light and middle REE in sediments of an estuary affected by phosphogypsum wastes (south-western Spain)

Sc, Y, Th, Cu and rare earth elements (REE) concentrations have been analyzed in 14 samples of surface sediments and in two gravity cores by means of ICP-MS. Mean concentrations of Sc, Y and Th in surface sediments are 6.23, 4.76 and 16.30 ppm, respectively, lower than those present in the Upper Continental Crust (UCC). Cu concentration in these sediments is very high, 1466 ppm, and is caused by inputs from the Odiel and Tinto rivers, affected by acid mine drainage. SigmaREE mean concentration is 106.8 ppm, lower than that observed in other rivers and estuaries. In the cores, Sc, Y and Th concentrations show a significant increase in the intermediate levels, between 10 and 40 cm depth. The same pattern exists with Cu, where concentrations of 4440 ppm can be reached. Vertical evolution patterns for Sc, Y, Cu and heavy REE (HREE) are similar, and contrary to those shown by Th, light REE (LREE) and middle REE (MREE). Plots of North American Shale Composite (NASC)-normalized REE data of surface sediments show a slight depletion in REE concentrations. Most samples present with middle REE enrichment relative to light REE and heavy REE. Conversely, samples of the intermediate levels of the cores show significant enrichment of REE relative to NASC and high values in the (La/Gd)NASC and (La/Yb)NASC ratios. These anomalies in the fractionation patterns caused by enrichments in LREE and MREE concentrations is related to the presence of high concentrations of Th. They were generated by effluents from fertilizer factories between 1968 and 1998 which used phosphorite as source material.