Low-Pressure Photoionization in a Dual-Ion Funnel Injector Coupled to an Orbitrap Mass Spectrometer for Direct Analysis of Human Breath and Head-Space Sampled Coffee Roasts

Bookmeyer C, Soltwisch J, Röhling U, Dreisewerd K

Abstract

Abstract Low‐pressure photoionization (LPPI) is a versatile tool for the mass spectrometric detection of (semi‐)volatile organic compounds, (s)VOC. Here, a dual‐ion funnel MALDI/ESI ion injector was equipped with a direct‐inlet LPPI module. A radio‐frequency (RF) drive enabled the implementation of three Kr discharge lamps in a novel design optimized for efficient photoionization and undisturbed ion trajectories. Supported by expansion and collisional cooling and, optionally, dopant vapor, primarily intact radical ions and protonated molecules were generated. Molecular identification was supported by the high‐resolving power of an Orbitrap mass analyzer. In our proof‐of‐concept study, exhaled human breath and head‐space sampled coffee grounds were characterized with this high‐throughput technique. From breath, a few hundred and for the coffee roasts more than thousand distinct (s)VOC features were recorded. Principal component analysis enabled the differentiation of coffee grounds by origin and roasting protocol.