Evaluation of the Chelex-DGT technique for the measurement of rare earth elements in the porewater of estuarine and marine sediments

Abstract

This study describes the validation of a diffusive gradients in thin film (DGT) technique for determining lanthanide rare earth elements (REEs) and in situ measurements of REEs in sediment pore waters. Laboratory experiments demonstrated that Chelex-100 binding layers had uptake efficiencies ranging from 78.0% to 92.3% for all REEs. An eluent of 1 mol L−1 HNO3 was optimal with elution efficiencies >80% for all REEs. Mass versus time experiments confirmed that DGT uptake was linear for all REEs at pH 8.1, 6.6 and 3.9 over a period of 3–4 days. Diffusion coefficients (D) for all REEs were derived from these experiments using the slopes of the linear regressions. D values varied with pH but were generally similar to values reported previously. The Chelex-100 DGT technique from this study is highly sensitive for the measurement of REE concentrations with detection limits ranging from 1.8 to 45 ng L−1 based on 72 h deployments allowing measurements of natural trace REE levels. Chelex-100 DGT devices were deployed in estuarine and marine sediments over a period of 72 h and most REE porewater concentrations (50–10,410 ng L−1) were successfully measured. Individual depth profiles of REEs showed a complex response, with many peaks and troughs suggesting a high degree of sediment heterogeneity. Depth-averaged REE concentrations showed a typical zig-zag distribution, although patterns varied between sediment types, after the REEs were normalised using the Queensland Mud Composite shale reference. The Chelex-100 DGT technique therefore shows promise for REE measurements in sediments.