Determination of rare earth elements in seawater by inductively coupled plasma mass spectrometry with off-line column preconcentration using 2,6-diacetylpyridine functionalized Amberlite XAD-4

An off-line column preconcentration technique using a micro-column of 2,6 diacetylpyridine functionalized Amberlite XAD-4 with inductively coupled plasma mass spectrometry (ICP-MS) as a means of detection has been developed. The aim of the method was to determine rare earth elements (REEs) (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) in seawater. Sample solutions (2–10 mL) were passed through the column which was then washed with ultra-pure water to remove residual matrix. The adsorbed cations on the resin were eluted by using 2 mL of 0.1 mol L⁻¹ HNO₃ containing 10 ng mL⁻¹ indium as an internal standard. The eluent was analyzed for the metal concentrations using ICP-MS. Sample pH as well as the sample and eluent flow rates were optimized. The sorption capacity of resin was determined by the batch process, by equilibrating 0.05 g of the resin with solutions of 50 mL of 25 mg L⁻¹ of individual metal ions for 4 h at pH 6.0 at 26 °C. The sorption capacities for the resin were found to range between 47.3 μmol g⁻¹ (for Lu) and 136.7 μmol g⁻¹ (for Gd). Limits of detection (3σ), without any preconcentration, ranged from 2 ng L⁻¹ to 10.3 ng L⁻¹ (for Tm and Lu respectively). The proposed method was applied to the determination of REEs in seawater and tap water samples.