Dissolved metal ion removal by online hollow fiber ultrafiltration for enhanced size characterization of metal-containing nanoparticles with single-particle ICP-MS

Abstract

Single particle-inductively coupled plasma mass spectrometry (SP-ICP-MS) is a powerful tool for size-characterization of metal-containing nanoparticles (MCNs) at environmentally relevant concentrations, however, coexisting dissolved metal ions greatly interfere with the accuracy of particle size analysis. The purpose of this study is to develop an online technique that couples hollow fiber ultrafiltration (HFUF) with SP-ICP-MS to improve the accuracy and size detection limit of MCNs by removing metal ions from suspensions of MCNs. Through systematic optimization of conditions including the type and concentration of surfactant and complexing agent, carrier pH, and ion cleaning time, HFUF completely removes metal ions but retains the MCNs in suspension. The optimal conditions include using a mixture of 0.05 vol.% FL-70 and 0.5 mmol/L Na2S2O3 (pH = 8.0) as the carrier and 4 min as the ion cleaning time. At these conditions, HFUF-SP-ICP-MS accurately determines the sizes of MCNs, and the results agree with the size distribution determined by transmission electron microscopy, even when metal ions also are present in the sample. In addition, reducing the ionic background through HFUF also lowers the particle size detection limit with SP-ICP-MS (e.g., from 28.3 to 14.2 nm for gold nanoparticles). This size-based ion-removal principle provided by HFUF is suitable for both cations (e.g., Ag+) and anions (e.g., AuCl4−) and thus has good versatility compared to ion exchange purification and promising prospects for the removal of salts and macromolecules before single particle analysis.