Distribution and fractionation of rare earth elements in suspended particulate matter in a coastal river, Southeast China

BACKGROUND: In the river system, the geochemistry of rare earth elements (REEs, a series of elements from La to Lu) in suspended particulate matter (SPM) is generally controlled by rock weathering processes and hydrochemical characteristics, as well as being affected by anthropogenic activities. However, the variations of geochemical characteristics and behaviors of REEs in SPM with a salinity gradient from the inland river to the estuary have been short of a systematic understanding. METHODS: The REE concentrations, Post Archean Australia Shale (PAAS)-normalized REE, La/Yb, La/Sm, and Sm/Yb ratios of SPM were investigated in the Jiulongjiang River, which is a coastal river mainly flowing through granite rocks in Southeast China. The correlation relationships between physicochemical parameters (including water pH, total dissolved solids (TDS), HCO(3)(–) concentrations, and the concentrations of major elements of SPM) and PAAS-normalized REE ratios of SPM were analyzed to determine the factors that affect the REE concentration and fractionation of SPM in the different regions of Jiulongjiang River, including the main stream and tributary of Beixi River, Xixi River, Nanxi River, and estuary. Additionally, the Ce, Eu, and Gd anomalies of SPM were estimated. RESULTS: The average ∑REE concentration of SPM (352 mg/kg) in the granite rock basin was twice higher than the mean value (175 mg/kg) of the world’s rivers. The PAAS-normalized REE ratios of SPM in the main rivers including Beixi River (main stream), Xixi River, and Nanxi River were near due to the same lithologic distribution. In the tributary of Beixi River, the input of low-weathered carbonate minerals which contain very few REE caused the lower REE concentrations of SPM. The PAAS-normalized REE ratios of SPM in the estuary were significantly lower than those in the main rivers, which was mainly attributed to the significant REE removal with the increment of salinity. The enrichment of LREE relative to HREE in SPM increased with decreasing water pH in the main rivers. In the estuary, the preferential removal of dissolved LREE occurred compared to HREE with the increment of salinity. The negative Ce and Eu anomalies of SPM occurred in both the main rivers and estuary region and rare Gd pollution was present in the basin. Additionally, human activities caused the increment of REE concentrations and more negative Ce anomaly at some specific sites, such as dam effect and agricultural pollution. CONCLUSIONS: The REE concentrations and fractionations of SPM in river water mainly depend on lithologic distribution and riverine pH, while they are affected by salinity in the estuary.