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

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.