Laboratory calibration and field testing of the Chemcatcher-Metal for trace levels of rare earth elements in estuarine waters

Little knowledge is available about water concentrations of rare earth elements (REEs) in the marine environment. The direct measurement of REEs in coastal waters is a challenging task due to their ultra-low concentrations as well as the high salt content in the water samples. To quantify these elements at environmental concentrations (pg L⁻¹ to low ng L⁻¹) in coastal waters, current analytical techniques are generally expensive and time consuming, and require complex chemical preconcentration procedures. Therefore, an integrative passive sampler was tested as a more economic alternative sampling approach for REE analysis. We used a Chemcatcher-Metal passive sampler consisting of a 3M Empore Chelating Disk as the receiving phase, as well as a cellulose acetate membrane as the diffusion-limiting layer. The effect of water turbulence and temperature on the uptake rates of REEs was analyzed during 14-day calibration experiments by a flow-through exposure tank system. The sampling rates were in the range of 0.42 mL h⁻¹ (13 °C; 0.25 m s⁻¹) to 4.01 mL h⁻¹ (13 °C; 1 m s⁻¹). Similar results were obtained for the different REEs under investigation. The water turbulence was the most important influence on uptake. The uptake rates were appropriate to ascertain time-weighted average concentrations of REEs during a field experiment in the Elbe Estuary near Cuxhaven Harbor (exposure time 4 weeks). REE concentrations were determined to be in the range 0.2 to 13.8 ng L⁻¹, where the highest concentrations were found for neodymium and samarium. In comparison, most of the spot samples measured along the Chemcatcher samples had REE concentrations below the limit of detection, in particular due to necessary dilution to minimize the analytical problems that arise with the high salt content in marine water samples. This study was among the first efforts to measure REE levels in the field using a passive sampling approach. Our results suggest that passive samplers could be an effective tool to monitor ultra-trace concentrations of REEs in coastal waters with high salt content.