Deciphering the microheterogeneous repartition effect of environmental matrix on surface-enhanced Raman spectroscopy (SERS) analysis for pollutants in natural waters

Although surface-enhanced Raman spectroscopy (SERS) offers a promising technology for sensitive detection of environmental pollutants in natural waters, its performance can be greatly affected by the environmental matrix. The lack of identification of the origin and the underlying mechanism of matrix effect hinders the application of SERS in practical environmental analysis. Herein, with silver nanoparticles (AgNPs) as a solution-based SERS substrate, the matrix effect from environmental waters on SERS analysis and the underlying mechanisms were investigated. It was found that natural water matrix could deteriorate SERS performance and cause artefacts in SERS spectra. Among various aqueous components, natural organic matter (NOM), including humic substances and proteins, mainly contributed to the matrix effect on SERS detection, while polysaccharides or inorganic ions had minor influence. The matrix effect from NOM was found to be prevalent for different analytes and SERS substrates. The mechanism of the matrix effect from NOM in the ternary system of analyte, NOM, and nanoparticles was investigated through three mutual interactions. The microheterogeneous repartition of analytes by NOM, other than the formation of NOM-corona or competitive adsorption between NOM and analytes on nanoparticles, was found to play the dominating role in interfering with SERS detection. This work illuminates the origin and underlying mechanisms of the matrix effect, which will promote the practical application of SERS technology in environmental analysis.