Selective Labeling of Small Microplastics with SERS-Tags Based on Gold Nanostars: Method Optimization Using Polystyrene Beads and Application in Environmental Samples

Microplastics pollution is being unanimously recognized as a global concern in all environments. Routine analysis protocols foresee that samples, which are supposed to contain up to hundreds of microplastics, are eventually collected on nanoporous filters and inspected by microspectroscopy techniques like micro-FTIR or micro-Raman. All particles, whether made of plastic or not, must be inspected one by one to detect and count microplastics. This makes it extremely time-consuming, especially when Raman is adopted, and indeed mandatory for the small microplastic fraction. Inspired by the principles of cell labeling, the present study represents the first report in which gold nanostars (AuNS) are functionalized to act as SERS-tags and used to selectively couple to microplastics. The intrinsic bright signals provided by the SERS-tags are used to run a quick scan over a wide filter area with roughly 2 orders of magnitude shorter analysis time in respect of state of the art in micro- and nanoplastics detection by μ-Raman. The applicability of the present protocol has been validated at the proof-of-concept level on both fabricated and real offshore marine samples. It is indeed worth mentioning that a SERS-based approach is herein successfully applied on filters and protocols routinely adopted in environmental microplastics monitoring, paving the way for future implementations and applications.