Incidental ultrafine particles (UFPs) constitute a key pollutant in industrial workplaces. However, characterizing their chemical properties for exposure and toxicity assessments still remains a challenge. In this work, the performance of an aerosol concentrator (Versatile Aerosol Concentration Enrichment System, VACES) was assessed to simultaneously sample UFPs on filter substrates (for chemical analysis) and as liquid suspensions (for toxicity assessment), in a high UFP concentration scenario. An industrial case study was selected where metal-containing UFPs were emitted during thermal spraying of ceramic coatings. Results evidenced the comparability of the VACES system with online monitors in terms of UFP particle mass (for concentrations up to 95 µg UFP/m3) and between filters and liquid suspensions, in terms of particle composition (for concentrations up to 1000 µg/m3). This supports the applicability of this tool for UFP collection in view of chemical and toxicological characterization for incidental UFPs. In the industrial setting evaluated, results showed that the spraying temperature was a driver of fractionation of metals between UF (<0.2 µm) and fine (0.2-2.5 µm) particles. Potentially health hazardous metals (Ni, Cr) were enriched in UFPs and depleted in the fine particle fraction. Metals vaporized at high temperatures and concentrated in the UF fraction through nucleation processes. Results evidenced the need to understand incidental particle formation mechanisms due to their direct implications on particle composition and, thus, exposure. It is advisable that personal exposure and subsequent risk assessments in occupational settings should include dedicated metrics to monitor UFPs (especially, incidental).