Laser Ablation for Nondestructive Sampling of Microplastics in Single-Particle ICP-Mass Spectrometry

In this work, laser ablation (LA) was characterized as a method for sampling and introducing microplastic particles (MPs) into an inductively coupled plasma (ICP) for subsequent ¹³C⁺ monitoring using an ICP-mass spectrometer operated in single-event mode. MPs of different types (PS, PMMA, and PVC) and sizes (2-20 μm) were introduced intactly. The laser energy density did not affect the particle sampling across a wide range (0.25-6.00 J cm^-2). Single-shot analysis separated clustered MPs (2-7 MPs per cluster) during the LA and particle transport processes, allowing the temporally resolved analysis of the individual constituting MPs. Line scanning showed superior performance when using a small laser beam diameter combined with a high repetition rate. The ¹³C⁺ signal intensity correlated linearly (R² >0.9945) with the absolute C mass in a 2-10 μm size range, while the use of He in the collision-reaction cell (CRC) allowed extension of the linear range to 20 μm. The LA approach generated narrower ¹³C⁺ signal distributions than the traditional solution-based approach (dry versus wet plasma conditions) and proved successful for the analysis of a mixed suspension (containing four sizes of PS MPs in a 2-5 μm size range) and for sampling MPs from PVDF and glass microfiber filters, with the latter offering a lower background.