By coupling thin-film microextraction (TFME) with surface-enhanced Raman scattering (SERS), a facile method was developed for the determination of sulfur dioxide (SO2), the most effective food additive in winemaking technology. The TFME substrate was made by free settling of sea urchin-like ZnO nanomaterials on a glass sheet. The headspace sampling (HS) procedure for SO2 was performed in a simple homemade device, and then the SO2 was determined using SERS after uniformly dropping or spraying a SERS-active substrate (gold nanoparticles, AuNPs) onto the surface of the TFME substrate. A reproducible and strong SERS response of the SO2 absorbed onto the ZnO substrate was obtained. After condition optimization, the SERS signal intensity at a shift of 600 cm(-1) and the SO2 concentration showed a good linearity in the range of 1-200 μg/mL, and the linear correlation coefficient was 0.992. The detection limit for SO2 was found to be 0.1 μg/mL. The HS-TFME-SERS method was applied for the determination of SO2 in wine, and the results obtained agreed very well with those obtained using the traditional distillation and titration method. Analysis of variance and Student t test show that there is no significant difference between the two methods, indicating that the newly developed method is fast, convenient, sensitive and has selective characteristics in the determination of SO2 in wine.

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