Magnetic Sector ICPMS with Desolvating Micronebulization: Interference-Free Subpicogram Determination of Rare Earth Elements in Natural Samples

Abstract

A new method has been developed combining desolvating micronebulization with magnetic sector inductively coupled plasma mass spectrometry (ICPMS) for the analysis of all 14 stable rare earth elements (REEs) in small samples of marine particulate matter. Application is demonstrated for REEs in suspended particles from a deep ocean hydrothermal vent plume and a geological reference material. A 100-fold reduction in oxide formation, relative to standard nebulizer-spray chamber sample introduction, makes oxide interference correction negligible, even for samples that are very enriched in Ba and light REEs. Enriched isotopes for one light and one heavy REE ((145)Nd and (171)Yb) are used as both isotope dilution and internal standards, providing determination of all the REEs in one analysis. This standardization scheme eliminates the need for multimass drift correction used previously to achieve acceptable accuracy with external standardization techniques. Instead, the method exploits capabilities for accurate and precise determination of isotope ratios, a principal strength of ICPMS, and the mass-independent sensitivity of electric field scans on our double-focusing instrument. We demonstrate overall precision of ≤2% (1σ) and accuracy better than 6% for all the REEs (except Er = 8.7%), based on comparison to recommended values for USGS certified reference material BHVO-1 (basalt). This performance is similar to that obtained by full isotope dilution mass spectrometric techniques, but the new method is far simpler, requires 5 min sample(-)(1), and avoids interferences introduced by complex mixtures of enriched isotopes. Sensitivity of (1.2-1.4) × 10(6) counts s(-)(1) ppb(-)(1) and background intensities of 2-60 counts s(-)(1) provide excellent detection limits of 1-40 ppq, a 100-fold improvement on established ICPMS methods. The low sample introduction rate (100 μL min(-)(1)) allows unprecedented absolute detection limits of 1-20 fg.