Validation of microwave acid digestion, diffusive gradients in thin-film preconcentration and inductively coupled plasma optical emission spectrometry methodology for the determination of REEs in natural zeolites

Abstract

The determination of rare earth element (REE) content in different natural minerals is of high interest due to their extensive use in modern and sustainable technologies. The REEs occurring in natural zeolites are specific to each deposit. This study presents the validation and evaluation of the measurement uncertainty for the determination of REEs (Ce, Dy, Er, Eu, Gd, La, Lu, Nd, Pr, Sm, Y, and Yb) in natural zeolites using microwave-assisted acid digestion and inductively coupled plasma optical emission spectrometry (ICP-OES) after diffusive gradients in thin-film preconcentration. A mixture of HNO₃ : HCl : HF of 3 : 9 : 2 (v/v/v) and microwave digestion provided suitable recoveries for the analysis of two certified reference materials, CRM BCS-CRM 375/1 and CRM OREAS 460. Good linearity over the calibration range of 0–2 μg mL⁻¹, with correlation coefficients of 0.9995–1.0000, was obtained for each REE by ICP-OES. The limits of quantification (LOQ_S), calculated considering the instrumental LOQs and the sample preparation by microwave digestion, were in the range of 0.20–0.60 mg kg⁻¹. A supplementary step of preconcentration/matrix separation based on the passive sampling by diffusive gradients in thin-films (DGT) technique improved the LOQs by about 20 times after three days of passive accumulation, allowing the measurement of the concentrations of all studied REEs in natural zeolite samples. The proposed methodology is a suitable approach for the measurement of REEs at low concentrations in natural zeolite samples by ICP-OES, and it can be extended to other geological samples. The measurement uncertainty was calculated based on the validation data. The proposed method provides reliable results for the measurement of REEs in natural zeolites and was used to measure the specific concentrations of REEs in natural zeolite samples from three Romanian quarries. The REE concentration can be used as a fingerprint for each deposit.