Enrichment and Fractionation of Rare Earth Elements in an Estuarine Marsh Soil Receiving Acid Discharges from Legacy Sulfide Mine Wastes

Abstract

This paper provides new insights into the geochemical cycling of rare earth elements (REEs) in acid sulfate soils developed on salt marsh sediments of the Huelva estuary (Spain) as a result of sulfide mineral oxidation in abandoned ore stockpiles. The study was aimed at determining the REE abundance, fractionation pattern and mineralogical control of the dispersal and retention of REEs in the soil system. Forty-one samples were collected at 13 core sampling sites along two transects extending across the degraded marshland, and they were subjected to XRD, ESEM-EDS and ICP-MS analyses. Measurements revealed that the soil receiving acid discharges has relatively high concentrations of ΣREEs (174.77 ± 19.77 mg kg−1) compared to local baseline concentrations. Shale-normalized REE patterns are generally flat, but a slight middle REE (MREE) enrichment is consistently apparent in all soil samples, involving relatively low LaN/GdN ratios (0.83 ± 0.08) and GdN/LuN ratios up to 1.42. The convex-upward REE pattern supports the possibility that iron oxy-hydroxide minerals play an important role in MREE retention through adsorption and co-precipitation mechanisms. Efflorescent sulfate salts left on the topsoil by the evaporation of acid waters show a strong depletion of light REEs (LaN/GdN = 0.16 ± 0.10) and act as a temporary reservoir of labile MREEs and heavy REEs during dry periods.