Accurate determination of ultra-trace REEs in seawater using a membrane desolvation Q-ICP-MS coupled with an online automatic separation system†

Abstract

The determination of rare earth elements (REEs) in seawater, especially marine sediment porewater and open-ocean seawater, is challenging because of their ultra-trace concentrations (ng L⁻¹ to pg L⁻¹) and the high salinity of the matrix (approximately 35‰ NaCl), which limits their application in marine science. Herein, we developed an online method for accurate analysis of ultra-trace REEs in seawater using a traditional Q-ICP-MS. The key aspects were: (i) high sensitivity detection in standard mode with no collision/reaction cell functioned, (ii) online automated matrix removal and preconcentration using a commercially available seaFAST system, (iii) use of membrane desolvation to enhance the sensitivity and limit the interferences of LREE oxides on HREEs, and (iv) monitoring and correction of variations in REE signal intensities caused by instrument drift using standard–samples–standard bracketing and an indium internal standard for normalization. The detection limits (0.1–8.0 pg L⁻¹) and procedural blank values (<3 pg L⁻¹ except for La, Ce, and Nd) of this method were low enough for accurate determination of REEs in seawater, even for REE concentrations at tens of picograms per liter level. The good accuracy and long-term precision (30 h, average: 3.5%, 1σ RSD, n = 10) were achieved for all the REEs as verified using certified seawater reference standards NASS-7 and CASS-6, and a 10 ng L⁻¹ artificial seawater standard, respectively. Each run required only approximately 8 mL of sample and 12 min for the measurement, which are suitable values for practical application. The developed method was used to analyze various natural seawater samples, which demonstrated its effectiveness for exploring subtle changes in REE concentrations, fractionation patterns and anomalies in different marine environments.