Fast On-Site Speciation and High Spatial Resolution Imaging of Labile Arsenic in Freshwater and Sediment Using the DGT-SERS Sensor

Diffusive gradients in thin films (DGT) technique is renowned for in situ passive sampling but not for rapid on-site analysis, whereas surface-enhanced Raman spectroscopy (SERS) excels in ultrasensitive on-site detection but is limited by substrate contamination from complex matrices. Here, a hierarchical nanostructure of silver (Ag) mirror-supported large Ag nanoparticles (∼120 nm) was grown in situ in polyacrylamide hydrogel with a restricted pore size (PAM/Ag mirror/AgNPs) to serve as both the DGT binding phase and the SERS substrate. The substrate exhibited a maximum electric field enhancement factor of 9.9 × 108 and a signal relative standard error of 4.8%. Using the DGT-SERS sensor, As(III) and As(V) in freshwater were simultaneously detected at limits of 0.9 and 0.8 μg L–1, respectively, applicable across a wide range of environmental conditions. The DGT-SERS effectively mitigated the interfacial reduction of As(V) caused by humic acid by excluding it from plasmonic hotspots through size exclusion of the diffusive layer. The Raman analysis of a DGT sample in the field requires only 2 s using a portable spectrometer without DGT device disassembly. More importantly, the DGT-SERS captured the first two-dimensional image of As(III) and As(V) in one DGT at the micron scale resolution, revealing their spatially supplementary distribution patterns at the sediment-water interface. This study paves the way for next-generation speciation imaging DGT and the application of SERS in complex environments.