3D-printed SPME-based wooden-tip mass spectrometry for rapid detection of organic ultraviolet absorbers in complex...

Organic ultraviolet absorbers (OUVs), commonly used in sunscreens and industrial products, have raised growing environmental and health concerns due to their pervasive occurrence in aquatic ecosystems. Conventional analytical techniques, such as liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS), offer high sensitivity but are constrained by labor-intensive workflows and extensive solvent use. Here, we present a rapid and portable screening method for seven priority OUVs by integrating a C₁₈-modified wooden-tip solid-phase microextraction (SPME) probe with ambient mass spectrometry (AMS). A custom-designed 3D-printed interface was designed to precisely align the ionization source with the mass spectrometer, enhancing stability, reproducibility, and operational ease. Detection limits (LODs) ranged from 0.23 μg/L to 8.17 μg/L, sufficient for high-exposure scenarios such as recreational waters (up to μg/L level) and the permitted concentration range in personal care products (typically 2-10 %, w/w). While the sensitivity is lower than that of LC-MS or GC-MS, the method achieves comparable extraction recoveries (81.3-119.6 %) in ultrapure water and post-cleansing facial rinses. In artificial seawater, recoveries dropped to 50.9-83.0 % due to salt and organic matter interfering with ionization. Despite this, the total analysis time was significantly reduced-from hours to minutes-without complex sample preparation. Field applications demonstrate the method's practicality: (1) OUVs in commercial sunscreens matched labeled ingredients; (2) surfactant-assisted cleansing increased OUV release from the skin by 1.58-2.31 times compared to water rinsing; and (3) benzophenone-1 (BP-1), 2-ethylhexyl-4-methoxycinnamate (EHMC), and ethylhexyl dimethyl p-aminobenzoic acid (ODPABA) were detected in swimming pool and coral reef waters, with concentrations up to 55.59 μg/L. This study provides an efficient, low-cost, and environmentally friendly alternative for rapid OUV screening and environmental risk assessment.