Dissolved rare earth elements in the Pearl River Delta : Using Gd as a tracer of anthropogenic activity from river towards the sea

Growing demands for high-tech uses of rare earth elements (REE) result in their releases into the aquatic environment, but local anthropogenic sources and water chemistry reactions may vary in aquatic systems. In this study, we quantified the yttrium and REEs (REY) in the surface waters of the Pearl River Delta (PRD), Southern China, and investigated their sources and processes controlling the dissolved REY distributions from rivers towards the sea. Spatial variations of dissolved REY concentrations (<0.4 μm) were observed in the surface water due to both natural and anthropogenic sources. Salt-induced flocculation removed colloidal REY from water during estuarine mixing, particularly at low salinity. In contrast, a significant increase of dissolved REY concentration with salinity suggested the occurrence of REY desorption from particles during estuarine mixing. The PAAS-normalized REE patterns (i.e., filtrates <0.4 μm and <3 kDa) showed a significant light REE (LREE) depletion relative to heavy REE (HREE) in dissolved fractions, indicating reactive LREE adsorption onto particles. Positive Gd anomalies in most waters revealed significant impacts from human activities, such as effluents from wastewater treatment plants in the PRD. In particular, the anthropogenic Gd contributed 90 % of the total dissolved Gd along the Pearl River and was conservatively mixed with saltwater in the estuary via the Humen outlet. Positive Sm anomalies were also observed in the PRD, indicating other point sources related to industrial activity. With the increase of urbanization and high demand for green technology, the REY anomalies could be a good indicator of human activities on assessing their fluxes and impacts on the aquatic systems.