Robust, reliable and quantitative sensing of aqueous arsenic species by Surface-enhanced Raman Spectroscopy: The crucial role of surface silver ions for good analytical practice

Arsenic speciation analysis is important for pollution and health risk assessment. Surface-enhanced Raman Spectroscopy (SERS) is supposed to be a promising detection technology for arsenic species owing to the unique fingerprints. However, further application of SERS is hampered by its poor repeatability. Herein, the role of surface silver ions on colloidal Ag was revealed in SERS analysis of arsenic species. Arsenic species were adsorbed on Ag nanoparticles (Ag NPs) driven by surface silver ions and were simultaneously sensed by the SERS "hot spots" generated from the aggregation of Ag NPs. So, the inconsistent SERS activities of Ag NPs synthesized from different batches can be significantly improved by modifying external silver ions onto Ag NPs (AgNPs@Ag+), Specific binding affinity of surface silver ions to arsenic species generated higher sensitivity (detection limit, 4.0 × 10-11 mol L-1 for arsenite, 8.0 × 10-11 mol L-1 for arsenate), wider linear range, faster response, cleaner spectra background and better reproducibility. Batch-to-batch reproducibility was significantly improved with a variation below 3.1%. The method was also demonstrated with drinking and environmental water with adequate recovery and high interference resistance. Our findings displayed good analytical practice of the surface silver ions derived SERS method and its great potential in the rapid detection of hazardous materials.