Rare earth elements in the Rhine River, Germany: first case of anthropogenic lanthanum as a dissolved microcontaminant in the hydrosphere

The distribution of dissolved rare earth elements (REE) in the Rhine River, Germany, shows the anthropogenic gadolinium (Gd) microcontamination that is commonly observed in rivers in densely populated countries with a highly evolved health care system. However, the Rhine River also carries anomalously high concentrations of lanthanum (La), which produce very large positive La anomalies in normalized REE distribution patterns. These positive La anomalies first occur north of the City of Worms and then decrease in size downstream, but are still significant approximately 400 km downstream, close to the German-Dutch border. The strong La enrichment is of anthropogenic origin and can be traced back to effluent from a production plant for fluid catalytic cracking catalysts at Rhine river-km 447.4. This effluent is characterized by extremely high dissolved total REE and La concentrations of up to 52 mg/kg and 49 mg/kg, respectively. Such La concentrations are well-above those at which ecotoxicological effects have been observed. The Rhine River is the first case observed to date, where a river's dissolved REE inventory is affected and even dominated by anthropogenic La. Our results suggest that almost 1.5t of anthropogenic dissolved La is exported via the Rhine River into the North Sea per year. This reveals that the growing industrial use of REE (and other formerly "exotic" elements) results in their increasing release into the environment, and highlights the urgent need to determine their geogenic background concentrations in terrestrial surface waters.