Detecting antimony(III) on-site using novel gel-based techniques: Colorimetric diffusive equilibrium in thin films for two-dimensional imaging and surface-enhanced Raman scattering for sensitive quantification

Antimony (Sb) pollution has raised increasing public concerns and its rapid on-site screening is central for the risk assessment. Herein, we proposed two gel-based methods based on colorimetric diffusive equilibrium in thin films (DET) and surface-enhanced Raman scattering (SERS), for two-dimensional imaging and sensitive detection of Sb(III) by revisiting the phenylfluorone (PhF) complexation reaction. PhF was well dispersed in the polyvinyl alcohol (PVA) hydrogel and reacted with Sb(III) in the DET gel to form a strong PhF-Sb(III) complex. The distribution of Sb(III) was easily visualized at a submillimeter resolution using computer imaging densitometry, with a detection limit (LOD) of similar to 100 nmol L-1. Field application in the Sb mine area reveals limited dissolved Sb(III) penetrating the redox barrier below the sediment-water interface by 20 mm in rivers and tailing pond sediments. To improve the detection sensitivity and apply the principle to trace Sb quantification, a SERS platform was established by anchoring PhF on the hydrogel-stabilized Ag nanoparticles via C-O-Ag bonding to specifically detect Raman-inactive Sb(III). Benefiting from the high SERS activity of PhF and enrichment ability of hydrogel, Sb(III) was quantified with a LOD of 1.2-10.7 nmol L-1 depending on the sample volume. The coexisting ions at a 100-fold higher concentration than Sb(III) resulted in only 3.3-10.4 % variation in SERS intensity, indicating a negligible interference on the SERS platform. The platform exhibited a RSD of 6.6-13.1 % and acceptable recoveries for various environmental matrices, highlighting its promise in on-site application.